Hetarylalkenes, their preparation and intermediates for their preparation and their use

ABSTRACT

Hetarylalkenes of the general formula I   &lt;IMAGE&gt; I  where Ar is hetaryl, A is C1-C6-alkyl, C2-C6-alkenyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C3-alkyl or unsubstituted or monosubstituted, disubstituted or trisubstituted aryl or aralkyl,  &lt;IMAGE&gt;  Z is where R is hydrogen, C2-C4-acyl, unsubstituted or substituted benzoyl, C1-C4-alkylsulfonyl, unsubstituted or C1-C4-alkyl-substituted phenylsulfonyl or a radical R1, R1 is C1-C4-alkyl or unsubstituted or substituted phenyl or benzyl and Hal is fluorine, chlorine, bromine or iodine, and B is unsubstituted or substituted mononuclear or dinuclear aryl, aralkyl or hetaryl, and their N-oxides and addition salts, the preparation of these substances, intermediates for this purpose and the preparation thereof, fungicides containing hetarylalkenes and a corresponding method for controlling harmful fungi.

The present invention relates to novel hetarylalkenes of the generalformula I ##STR3## where Ar is 3-pyridyl, 3-pyridazinyl, 5-pyrimidinylor 2-pyrazinyl;

A is C_(1C) ₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₈ -cycloalkyl, CC₃ -C₈-cycloalkyl-C₁ -C₃ -alkyl, mononuclear, dinuclear or trinuclear aryl oraralkyl, where aryl in each case may be monosubstituted, disubstitutedor trisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -mono-, di-or trihaloalkyl, C₁ -C₄ -haloalkoxy, phenyl or halogen;

Z is ##STR4## where R is hydrogen, C₁ -C₄ -alkyl, C₂ --C₄ -acyl, phenyl,benzyl or benzoyl, in which each of the phenyl rings may bemonosubstituted, disubstituted or trisubstituted by C₁ -C₄ alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, halogen, cyano or nitro,or is C₁ -C₄ -alkylsulfonyl or unsubstituted or C₁ -C₄-alkyl-substituted phenylsulfonyl, R.sup. is C₁ -C₄ -alkyl, phenyl orbenzyl, where each of the phenyl rings may be monosubstituted,disubstituted or trisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, halogen, cyano or nitro, and Hal isfluorine, chlorine, bromine or iodine; and B is mononuclear or dinucleararyl, aralkyl or hetaryl, and, if Z is >CO, hetaryl has no sp³-hybrididized nitrogen atom directly adjacent to Z, and in which each ofthe aromatic rings may be monosubstituted, disubstituted ortrisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C.sub. 4-haloalkyl, C₂ -C₄ -haloalkoxy, phenyl, halophenyl or halogen, and theirN-oxides and addition salts with inorganic mineral acids, carboxylicacids or mononuclear arylsulfonic acids.

The present invention furthermore relates to processes for thepreparation of these compounds and also to intermediates, processes forthe preparation of intermediates, the fungicides containinghetarylalkenes I and a method for controlling harmful fungi with the aidof the hetarylalkenes I or these fungicides.

Fungicidal hetarylalkenes, for example ##STR5## are disclosed inEP-A2-104 690. However, the fungicidal action of most of these compoundsis unsatisfactory.

It is an object of the present invention to provide particularly activefungicidal compounds.

We have found that this object is achieved by the hetarylalkenes Idefined at the outset.

With regard to the intended use of the hetarylalkenes as fungicides,preferred substituents are the following radicals:

Ar is 3-pyridyl, 5-pyrimidinyl, 3-pyridazinyl or 2-pyrazinyl,

A is methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl,n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, cyclopropyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl,cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl,3-cyclohexylpropyl, phenyl, mono-, di- or trimethylphenyl,tert-butylphenyl, mono-, di- or trimethoxyphenyl, n-butoxyphenyl,tert-butoxyphenyl, trifluoromethylphenyl,difluoromethoxyphenyl,trifluoromethoxyphenyl,tetrafluoroethoxyphenyl,biphenyl, mono-, di- or trifluorophenyl, mono-, di- or trichlorophenyl,chlorofluorophenyl, benzyl, mono-, di- or trimethylbenzyl, mono-, di- ortrichlorobenzyl, fluorobenzyl, 2-phenylethyl, mono-, di- ortrimethylphenylethyl, mono-, di- or trichlorophenylethyl,fluorophenylethyl or 3-phenylpropyl,

B is phenyl, mono-, di or trimethylphenyl, ethylphenyl, isopropylphenyl,tert-butylphenyl, naphthyl, mono-, di- or trimethoxyphenyl,n-butoxyphenyl, tert-butoxyphenyl, trifluoromethylphenyl,difluoromethoxyphenyl, trifluoromethoxyphenyl, tetrafluoroethoxyphenyl,biphenyl, chlorobiphenyl, mono-, di- or trichlorophenyl, mono-, di- ortrifluorophenyl, chlorofluorophenyl, bromophenyl, benzyl, mono-, di- ortrimethylbenzyl, fluorobenzyl, mono-, di- or trichlorobenzyl,chlorofluorobenzyl, pyridyl, chloropyridyl, methylpyridyl, pyrimidinyl,pyrazinyl, thienyl or furyl

Z is ##STR6## where R is preferably hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, tert-butyl, acetyl, propionyl, butyryl, phenyl,mono-, di- or trimethylphenyl, tert-butylphenyl, mono-, di- ortrimethoxyphenyl, trifluoromethylphenyl, fluorophenyl, mono- ordichlorophenyl, bromophenyl, cyanophenyl, mono- or dinitrophenyl,benzyl, methylbenzyl, methoxybenzyl, trifluoromethylbenzyl,fluorobenzyl, mono- or dichlorobenzyl, bromobenzyl, cyanobenzyl, mono-or dinitrobenzyl, benzoyl, methylbenzoyl, fluorobenzoyl, mono-, di- ortrichlorobenzoyl, bromobenzoyl, cyanobenzoyl or mono- or dinitrobenzoyl,

R¹ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl,tert-butyl, phenyl, mono-, di- or trimethylphenyl, tert-butylphenyl,mono-, di- or trimethoxyphenyl, trifluoromethylphenyl, fluorophenyl,mono- or dichlorophenyl, bromophenyl, cyanophenyl, mono- ordinitrophenyl, benzyl, methylbenzyl, methoxybenzyl,trifluoromethylbenzyl, fluorobenzyl, mono- or dichlorobenzyl,bromobenzyl, cyanobenzyl or mono- or dinitrobenzyl

and Hal is, in particular, fluorine, chlorine or bromine.

Particularly preferred compounds are those in which A is ethyl,n-propyl, n-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, phenyl or4-fluorophenyl, B is phenyl, 2-chlorophenyl, 4-chlorophenyl,2,4-dichlorophenyl, 4-fluorophenyl, 2-methylphenyl, 4-methylphenyl,2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl,4-biphenyl or 3-pyridyl; and Ar is 3-pyridyl. Compounds which areparticularly suitable as fungicides areE-1-(2,4-dichlorophenyl)-2-(3-pyridylmethylidene)-4,4-dimethylpentan-1-ol,E-1-(2,4-dimethylphenyl)-2-(3-pyridylmethylidene)-hexan-1-ol,E-1-(2,4-dichlorophenyl)-2-(3-pyridylmethylidene)-3,3-dimethylbutan-1-ol,E-1-(2,4-dichlorophenyl)-2-(3-pyridylmethylidene)-hexan-1-ol andE-1-(2,4-dichlorophenyl)-2-(3-pyridylmethylidene)-octan-1-ol.

The hetarylalkenes I contain an asymmetrically substituted C═C doublebond. They can therefore occur as E/Z isomer mixtures or in the form ofthe pure isomers. The pure isomers can be obtained from the isomermixtures by known separation methods, such as fractional crystallizationor chromatography. The present invention relates both to the individualisomeric compounds and to mixtures thereof.

The hetarylalkenols Ia are obtained, for example, by reacting ahetarylalkenal II with an organolithium compound Li-B or with a Grignardreagent B-MgHal, where Hal is chlorine, bromine or iodine, in aconventional manner. The reaction is carried out in an inert solvent,preferably an ether, such as diethyl ether, tetrahydrofuran or methyltert-butyl ether or in a mixture of these ethers. It is advisableinitially to take the organometallic compound and to meter in thehetarylalkenal II in the liquid phase at from -70° to 50°C. In the caseof the organolithium compounds, the reaction is advantageously carriedout at from -70° to 0° C., preferably from -70° to -30°C. Thetemperatures in the reactions with the Grignard reagents are generallychosen at from 0° to 50° C., in particular from 20° to 50°C. The statedstarting materials are advantageously used in a molar ratio of from0.5:1 to 2:1.

The hetarylalkenals II, in which A is methyl or unsubstituted orsubstituted phenyl, are disclosed in J. Org. Chem. 43 (1978), 3396 andEP-A2-298 380. The novel hetarylalkenals II in which Ar is3-pyridazinyl, 5-pyrimidinyl or 2-pyrazinyl, preferably 3-pyridyl, and Dis C₂ -C₆ -alkyl, preferably ethyl, n-propyl, isopropyl, n-butyl ortert-butyl, C₃ -C₈ -cycloalkyl, in particular cyclopropyl, cyclopentylor cyclohexyl, C₃ -C₈ -cycloalkyl-C₁ -C₃ -alkyl, especiallycyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl,2-cyclohexylethyl or 3-cyclohexylpropyl, or mononuclear or dinucleararyl-C₁ -C₃ -alkyl, preferably benzyl, chlorobenzyl, fluorobenzyl,2-phenylethyl, chlorophenylethyl, fluorophenylethyl or 3-phenylpropyl,can be prepared similarly to the process disclosed in EP-A2-298 380, byaldol condensation of D-CH₂ CHO with ArCHO (cf. also Houben-Weyl,Methoden der organischen Chemie, Vol. III/1, page 76 et seq.).

The starting materials of the type D-CH₂ CHO are readily obtainablewhere D is alkyl and can be prepared by known methods (cf. Houben-Weyl,Volume 7/1, pages 55 et seq., 76 et seq., 159 et seq.) in the case ofthe other radicals.

3-Formylpyridine is generally known and readily obtainable. Thesyntheses of the other aldehydes of the type Ar--CHO are described in,for example, the standard work The Chemistry of Heterocyclic Compounds(A. Weissberger and E. C. Taylor) (3-formylpyridazine: The Pyridazines,R. N. Castle, Editor, page 365, John Wiley & Sons, New York, 1973;2-formylpyrazine: The Pyrazines, G. B. Barlin, Editor, page 294 et seq.,John Wiley & Sons, New York, 1982; 5-formylpyrimidine: The Pyrimidines,Suppl. I, D. J. Brown, page 127, John Wiley & Sons, New York, 1970).

The organometallic compounds Li-B and HalMgB can be prepared by knownprocesses, as described in Houben-Weyl, Methoden der organischen Chemie,Vol. XIII/1, page 87 et seq. and ibid. XIII/2a, page 54 et seq., fromB-Hal and Li or Mg.

In a second method for the preparation of the hetarylalkenols Ia, ahetarylaldehyde ArCHO is reacted with a ketone of the type ##STR7## togive the hetarylalkenone Ib. The hetarylalkenone Ib can then be reducedto the hetarylalkenol Ia by conventional methods. Ar, A and B have themeanings stated in claim 1.

The aldol condensation of the hetarylaldehyde ArCHO with the ketone##STR8## is carried out in the presence of a basic or acidic catalyst(cf. Houben-Weyl, Methoden der organischen Chemie, Vol. VII/1, page 76et seq.). Examples of suitable basic catalysts are alkali metal oralkaline earth metal hydroxides, such as sodium, potassium, calcium orbarium hydroxide, alkali metal alcoholates, such as sodium or potassiummethylate, ethylate, propylate or butylate, and amines, such asdiethylamine, triisopropylamine, dicyclohexylamine, pyrrolidine orpiperidine. Examples of suitable acidic catalysts are weak acids, suchas acetic acid, oxalic acid, boric acid and sulfonic acids, such asmethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid,and salts of weak acids with amines, such as piperidine acetate,pyrrolidine acetate, ethylenediamine tetraacetate, pyridinemethanesulfonate or pyridine p-toluenesulfonate.

Examples of suitable solvents are alcohols, such as methanol, ethanol,propanol, isopropanol, butanol or tert-butanol, ethers, such as diethylether, methyl tert-butyl ether, tetrahydrofuran or dioxane, orhydrocarbons, such as cyclohexane, benzene, toluene or xylene.

The reaction is carried out as a rule at from 0 to 60°C.

The molar ratio of the starting materials is from 0.5:1 to 5:1(ArCHO/ketone) and the molar ratio of ArCHO to the catalyst is from 1:1to 100:1.

The starting compounds of the type ##STR9## can be prepared, forexample, in a known manner from carbonyl chlorides and aromatics byFriedel-Crafts acylation (cf. Houben-Weyl, Volume 7/2a, page 15 etseq.).

The hetarylalkenones Ib can be reduced by conventional methods to thehetarylalkenols Ia already described (cf. Houben-Weyl, Methoden derorganischen Chemie, Vol. IV, 1d, page 297 et seq.). Examples of suitablereducing agents are complex hydrides, such as lithium aluminum hydride,lithium trimethoxyaluminum hydride, sodium borohydride or sodiumcyanoborohydride, and aluminum alcoholates, such as aluminumisopropylate or aluminum cyclohexylate (cf. M. Hudlicky, Reductions inOrganic Chemistry, page 119 et seq., Ellis Horward Series, Chichester,1984). The solvents used for the reductions are, for example, ethers,such as diethyl ether, tetrahydrofuran, dimethoxyethane or dioxane, oralcohols, such as methanol, ethanol, n-propanol, iso-propanol orcyclohexanol, depending on the reducing agent.

In the reduction with complex hydrides, it is advisable to carry out thereaction at from -30° to 20° C., whereas higher temperatures, inparticular the boiling point of the free alcohol from which the aluminumalcoholate is derivated, are advantageous when aluminum alcoholates areused.

Sodium borohydride or sodium cyanoborohydride in methanol or ethanol ispreferably used. The ratio of the number of equivalents ofhetarylalkenone Ib to reducing agent is, as a rule, from 1:1 to 1:2.

The novel hetarylalkenols Ia can be esterified or etherified to thehetarylalkene esters or ethers Ic. For this purpose, the hetarylalkenolsIa are reacted with alkylating or acylating agents R-X in a conventionalmanner (cf. Houben-Weyl, Volume 6/lb, pages 800 et seq., 823 et seq.).Here, R is C₁ -C₄ -alkyl, in particular methyl, ethyl, isopropyl ortert-butyl, C₂ -C₄ -acyl, preferably acetyl or propionyl, benzyl orbenzoyl, where the phenyl radicals may be monosubstituted, disubstitutedor trisubstituted by C₁ -C₄ -alkyl, such as methyl, ethyl, propyl orbutyl, C₁ -C₄ -alkoxy, such as methoxy, ethoxy or propoxy, C₁ -C₄-haloalkyl, especially trifluoromethyl, C₁ -C₄ -haloalkoxy, such astetrafluoroethoxy, halogen, such as fluorine, chlorine or bromine, cyanoor nitro, or is C₁ -C₄ -alkylsulfonyl, in particular methanesulfonyl orunsubstituted or C₁ -C₄ -alkyl-substituted phenylsulfonyl, and X is, forexample, chlorine, bromine, iodine, acetyl or, if R itself is not asulfo group, methanesulfonyl, benzenesulfonyl or p-toluenesulfonyl.

The reaction is carried out as a rule at from 0° to 100°C.

The type of solvent depends on the type of radical R. If. R is alkyl orbenzyl, preferably used solvents are ethers, such as diethyl ether,tetrahydrofuran, dioxane or dimethoxyethane, or amides, such asN,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylethyleneurea,N,N-dimethylpropyleneurea. An addition of an equimolar amount of a base,in particular sodium hydride, is also advisable.

If R is acyl, benzoyl or a sulfonyl halide, preferably used diluents arehalogenated or halogen-free hydrocarbons, such as dichloromethane ortrichloromethane, toluene or xylene, or an excess of a base which actsas a catalyst, preferably tertiary amines, such as triethylamine,tripropylamine or pyridine.

Hetarylalkene esters Ic in which R is sulfo can be converted intohetarylalkenes of the general formula Id by conventional methods (cf.Houben-Weyl, Vol. 9, page 343 et seq.) by reaction with halides,cyanides, hydrogen sulfides, alcohols or thiols.

Preferably used halides, cyanides or hydrogen sulfides are alkali metal,alkaline earth metal, ammonium or tetraalkylammonium salts. Examples arelithium cyanide, sodium cyanide, potassium cyanide, tetramethylammoniumcyanide, tetrabutylammonium cyanide, tetrabutylammonium fluoride,tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium iodide, lithium fluoride, lithium chloride, lithiumbromide, lithium iodide, sodium fluoride, sodium chloride, sodiumbromide, sodium iodide, potassium fluoride, potassium chloride,potassium bromide, potassium iodide, sodium hydrogen sulfide andpotassium hydrogen sulfide.

Particularly preferred alcohols are phenols which may bemonosubstituted, disubstituted or trisubstituted, inparticular phenol,mono-, di- or trimethylphenol, tertbutylphenol, mono-, di- ortrimethoxyphenol, trifluoromethylphenol, fluorophenol, chlorophenol orbromophenol.

Particularly suitable thiols are C₁ -C₄ -alkanethiols, such as methane-,ethane-, n-propane-, isopropane-, n-butane-, isobutane-, sec-butane- ortertbutanethiol, and unsubstituted or monosubstituted, disubstituted ortrisubstituted thiophenols or thiobenzyl alcohols, such as thiophenol,mono-, di- or trimethylthiophenol, tert-butylthiophenol, mono-, di- ortrimethoxythiophenol, fluoro- or chlorothiophenol, thiobenzyl alcohol,mono-, di- or trimethylthiobenzyl alcohol, tert-butylthiobenzyl alcohol,mono-, di- or trimethoxythiobenzyl alcohol, fluoro- or chlorothiobenzylalcohol or cyano- or nitrothiobenzyl alcohol.

Polar, inert solvents, such as ethers, especially tetrahydrofuran ordioxane, ketones, in particular acetone, methyl ethyl ketone or methylisobutyl ketone, nitriles, preferably acetonitrile or propionitrile,amides, for example N,N-dimethylformamide, N-methylpyrrolidone,N,N-dimethylethyleneurea or N,N-dimethylpropyleneurea, sulfoxides, inparticular dimethyl sulfoxide, sulfones, e.g. sulfolane, alcohols,preferably methanol, ethanol, n-propanol, isopropanol, n-butanol ortert-butanol, or mixtures of these substances are suitable for thereaction. In the reaction of the hetarylalkene esters Ic with phenols orthiols, auxiliary bases are used, especially alkali metal and alkalineearth metal hydroxides, such as sodium hydroxide or potassium hydroxide,alkali metal and alkaline earth metal carbonates, such as sodiumcarbonate, potassium carbonate or calcium carbonate, alkali metal andalkaline earth metal alcoholates, such as sodium methylate, sodiumethylate, sodium propylate, sodium isopropylate, potassium isopropylateor potassium tert-butylate, and tertiary amines, such as triethylamine,tripropylamine or pyridine.

The reaction is carried out as a rule at from 20° to 100°C.

The oxidation of the hetarylalkenes I to the corresponding N-oxides iscarried out by conventional methods. Examples of suitable oxidizingagents are per acids or per acids produced in situ from hydrogenperoxide and carboxylic anhydrides, or hydrogen peroxide or organicderivatives of hydrogen peroxide (cf. for example R. A. Abramovitch andE. M. Smith in Chemistry of Heterocyclic Compounds, Volume 14, Suppl. 2,page 1 et seq., John Wiley, New York, 1974; A. R. Katritzky and J. M.Lagouski, The Chemistry of Heterocyclic N-oxides, page 21 et seq.,Academic Press, New York, 1971).

The preparation of the acid addition salts of the hetarylalkenes I islikewise carried out by conventional methods.

An overview of the stated preparation processes for the hetarylalkenes Iis shown in the scheme below: ##STR10##

The Examples which follow illustrate the preparation of the novelcompounds.

1. Preparation ofE-1-(4-fluorophenyl)-2-(3-pyridylmethylidene)-1-hexanol viaE-2-(3-pyridylmethylidene)-hexanal

6.0 g (0.15 mol) of sodium hydroxide were added to a solution of 160.5 g(1.5 mol) of pyridine-3-carbaldehyde in 750 ml of methanol. Thereafter,150.0 g (1.5 mol) of hexanal were added dropwise in the course of 3hours at room temperature. Stirring was carried out for 1 hour, the pHwas brought to 6 with acetic acid and the solvent was then evaporatedunder reduced pressure. The residue was taken up in awater/dichloromethane mixture and the organic phase was washed withwater, dried over sodium sulfate and evaporated down under reducedpressure. Distillation gave 190 g (67% of theory) ofE-2-(3-pyridylmethylidene)-hexanal as a yellow oil of boiling point132°-134° C./2 mbar.

From 4.1 g (0.17 mol) of magnesium turnings which had been activatedwith 1 ml of 1,2-dibromomethane, a Grignard solution was prepared by thedropwise addition of a solution of 29.8 g (0.17 mol) of4-fluorobromobenzene in 200 ml of tetrahydrofuran. Stirring was carriedout for 30 minutes at 50° C., after which 20.8 g (0.11 mol) of theE-2-(3-pyridylmethylidene)-hexanal prepared above, in 100 ml oftetrahydrofuran, were added dropwise. Stirring was continued for twohours at the reflux temperature, after which the mixture was cooled,hydrolysis was carried out with water and the pH was brought to 8 withsaturated NH₄ Cl solution. The aqueous phase was extracted with ether,and the combined organic phases were washed with water, dried over Na₂SO₄ and evaporated down under reduced pressure. 27.1 g. ofE-1-(4-fluorophenyl)-2-(3-pyridylmethylidene)-1-hexanol remained as ayellow oil having a purity of 94% according to gas chromatography(yield: 82% of theory; cf. Table, Example 290).

¹ H-NMR (CDCl₃) δ=8.40, 8.30, 7.58, 7.22 (2-, 6-, 4-, 5-H of thepyridine moiety), 7.38, 7.02 (2 H_(m) and 2 H_(o) of the aryl moiety),6.65 (C═CH), 5.30 (CHOH), 4.5 (OH), 2.20, 1.95 (3-CH₂), 1.23 ( 4- and5-CH₂), 0.78 (6-CH₃). IR (film): ν=3200, 2957, 2931, 2870, 1603, 1507,1222, 1155, 1028, 838, 713 cm⁻¹.

2 Preparation ofE-1-(2-chlorophenyl)-2-(4-fluorophenyl)-3-(3-pyridyl)-2-propen-1-one

A mixture of 24.9 g (0.10 mol) of 4-fluorobenzyl 2-chlorophenyl ketone,10.7 g (0.10 mol) of pyridine-3-carbaldehyde and 2.9 g (0.02 mol) ofpiperidine acetate in 250 ml of toluene was heated under a waterseparator until no further water separated off. After cooling, themixture was washed twice with saturated NaHCO₃ solution and with water,dried over sodium sulfate and evaporated down under reduced pressure.The residue was crystallized from 2:1 methyl tert-butyl ether/hexane.16.6 g (40% of theory) of a product were obtained in the form of yellowcrystals of melting point 102°0 C.

3. Preparation ofE-1-(2-chlorophenyl)-2-(4-fluorophenyl)-3-(3-pyridyl)-2-propen-1-ol

7.6 g (0.20 mol) of sodium borohydride were added a little at a time, at0° C., to a solution of 33.75 g (0.10 mol) of theE-1-(2-chlorophenyl)-2-(4-fluorophenyl)-3-(3-pyridyl)-2-propen-1-one,prepared under 2.), in 500 ml of methanol. Stirring was carried out for2 hours at 0° C., excess sodium borohydride was destroyed by thedropwise addition of acetic acid and the mixture was evaporated downunder reduced pressure. The residue was taken up in awater/dichloromethane mixture, and the organic phase was washed withwater, dried over sodium sulfate and evaporated down under reducedpressure. Trituration with 9:1 methyl tert-butyl ether/pentane gave 27.0g (79% of theory) of crystalline product of melting point 82°-83°C.(cf.Table, Example No. 682).

¹ H-NMR (CDCl₃) δ=8.20, 8.16, 7.48, 7.27 (6-, 2-, 4-, 5-H of thepyridine moiety), 7.20-6.90 (8 aryl-H), 6.70 (C═CH), 5.90 (CHOH).

The following compounds can be prepared similarly to these Examples:

                                      TABLE                                       __________________________________________________________________________     ##STR11##                                                                    Example                                                                       No.  A         B            Phys. data (Fp, IR, .sup.1 H-NMR)                 __________________________________________________________________________     1   CH.sub.3  Phenyl                                                          2   CH.sub.3  2-Methylphenyl                                                  3   CH.sub.3  3-Methylphenyl                                                  4   CH.sub.3  4-Methylphenyl                                                  5   CH.sub.3  2,4-Dimethylphenyl                                              6   CH.sub.3  2,6-Dimethylphenyl                                              7   CH.sub.3  2,4,6-Trimethylphenyl                                           8   CH.sub.3  4-Ethylphenyl                                                   9   CH.sub.3  4-Isopropylphenyl                                               10  CH.sub.3  4-tert-Butylphenyl                                              11  CH.sub.3  1-Naphthyl                                                      12  CH.sub.3  2-Naphthyl                                                      13  CH.sub.3  4-Biphenyl                                                      14  CH.sub.3  4-(2'-Chlorobiphenyl)                                           15  CH.sub.3  4-(4'-Chlorobiphenyl)                                           16  CH.sub.3  2-Methoxyphenyl                                                 17  CH.sub.3  3-Methoxyphenyl                                                 18  CH.sub.3  4-Methoxyphenyl                                                 19  CH.sub.3  3,4-Dimethoxyphenyl                                             20  CH.sub.3  3,4,5-Trimethoxyphenyl                                          21  CH.sub.3  4-tert-Butoxyphenyl                                             22  CH.sub.3  2-Trifluoromethylphenyl                                         23  CH.sub.3  3-Trifluoromethylphenyl                                         24  CH.sub.3  4-Trifluoromethylphenyl                                         25  CH.sub.3  4-Difluoromethoxyphenyl                                         26  CH.sub.3  4-Trifluoromethoxyphenyl                                        27  CH.sub.3  4-Tetrafluoroethoxyphenyl                                       28  CH.sub.3  2-Fluorophenyl                                                  29  CH.sub.3  3-Fluorophenyl                                                  30  CH.sub.3  4-Fluorophenyl                                                  31  CH.sub.3  2,4-Difluorophenyl                                              32  CH.sub.3  2-Chlorophenyl                                                  33  CH.sub.3  3-Chlorophenyl                                                  34  CH.sub.3  4-Chlorophenyl                                                  35  CH.sub.3  2,4-Dichlorophenyl                                              36  CH.sub.3  3,4-Dichlorophenyl                                              37  CH.sub.3  3,5-Dichlorophenyl                                              38  CH.sub.3  2,4,6-Trichlorophenyl                                           39  CH.sub.3  2-Chloro-4-fluorophenyl                                         40  CH.sub.3  4-Chloro-2-fluorophenyl                                         41  CH.sub.3  4-Bromophenyl                                                   42  CH.sub.3  Benzyl                                                          43  CH.sub.3  2-Methylbenzyl                                                  44  CH.sub.3  4-Methylbenzyl                                                  45  CH.sub.3  2,4-Dimethylbenzyl                                              46  CH.sub.3  2-Fluorobenzyl                                                  47  CH.sub.3  3-Fluorobenzyl                                                  48  CH.sub.3  4-Fluorobenzyl                                                  49  CH.sub.3  2-Chlorobenzyl                                                  50  CH.sub.3  3-Chlorobenzyl                                                  51  CH.sub.3  4-Chlorobenzyl                                                  52  CH.sub.3  2,4-Dichlorobenzyl                                              53  CH.sub.3  2-Chloro-4-fluorobenzyl                                         54  CH.sub.3  2-Pyridyl                                                       55  CH.sub.3  3-Pyridyl                                                       56  CH.sub.3  4-Pyridyl                                                       57  CH.sub.3  5-Methyl-2-pyridyl                                              58  CH.sub.3  6-Methyl-2-pyridyl                                              59  CH.sub.3  6-Chloro-3-pyridyl                                              60  CH.sub.3  5-Pyrimidinyl                                                   61  CH.sub.3  2-Pyrazinyl                                                     62  CH.sub.3  2-Thienyl                                                       63  CH.sub.3  3-Thienyl                                                       64  CH.sub.3  2-Furyl                                                         65  CH.sub.3  3-Furyl                                                         66  C.sub.2 H.sub.5                                                                         Phenyl       3219, 3084, 3060, 2967, 2874, 1452, 1046,                                     1026, 702                                          67  C.sub.2 H.sub. 5                                                                        2-Methylphenyl                                                  68  C.sub.2 H.sub.5                                                                         3-Methylphenyl                                                  69  C.sub.2 H.sub.5                                                                         4-Methylphenyl                                                  70  C.sub.2 H.sub.5                                                                         2,4-Dimethylphenyl                                                                         mp. 200-201° C.                             71  C.sub.2 H.sub.5                                                                         2,6-Dimethylphenyl                                                                         3227, 2964, 2933, 2874, 1468, 1412, 1076,                                     1027, 771, 713                                     72  C.sub.2 H.sub.5                                                                         2,4,6-Trimethylphenyl                                                                      mp. 178-180° C.                             73  C.sub.2 H.sub.5                                                                         4-Ethylphenyl                                                   74  C.sub.2 H.sub.5                                                                         4-Isopropylphenyl                                               75  C.sub.2 H.sub.5                                                                         4-tert-Butylphenyl                                              76  C.sub.2 H.sub.5                                                                         1-Naphthyl                                                      77  C.sub.2 H.sub.5                                                                         2-Naphthyl                                                      78  C.sub.2 H.sub.5                                                                         4-Biphenyl   3205, 3055, 3029, 2971, 1486, 1408, 1369,                                     1265, 764, 700                                     79  C.sub.2 H.sub.5                                                                         4-(2'-Chlorobiphenyl)                                           80  C.sub.2 H.sub.5                                                                         4-(4'-Chlorobiphenyl)                                           81  C.sub.2 H.sub.5                                                                         2-Methoxyphenyl                                                 82  C.sub.2 H.sub.5                                                                         3-Methoxyphenyl                                                 83  C.sub.2 H.sub.5                                                                         4-Methoxyphenyl                                                 84  C.sub.2 H.sub.5                                                                         3,4-Dimethoxyphenyl                                             85  C.sub.2 H.sub.5                                                                         3,4,5-Trimethoxyphenyl                                          86  C.sub.2 H.sub.5                                                                         4-tert-Butoxyphenyl                                             87  C.sub.2 H.sub.5                                                                         2-Trifluoromethylphenyl                                         88  C.sub.2 H.sub.5                                                                         3-Trifluoromethylphenyl                                         89  C.sub.2 H.sub.5                                                                         4-Trifluoromethylphenyl                                         90  C.sub.2 H.sub.5                                                                         4-Difluoromethoxyphenyl                                         91  C.sub.2 H.sub.5                                                                         4-Trifluoromethoxyphenyl                                        92  C.sub.2 H.sub.5                                                                         4-Tetrafluoroethoxyphenyl                                       93  C.sub.2 H.sub.5                                                                         2-Fluorophenyl                                                  94  C.sub.2 H.sub.5                                                                         3-Fluorophenyl                                                  95  C.sub.2 H.sub.5                                                                         4-Fluorophenyl                                                  96  C.sub.2 H.sub.5                                                                         2,4-Difluorophenyl                                              97  C.sub.2 H.sub.5                                                                         2-Chlorophenyl                                                  98  C.sub.2 H.sub.5                                                                         3-Chlorophenyl                                                  99  C.sub.2 H.sub.5                                                                         4-Chlorophenyl                                                                             mp. 185° C.                                100  C.sub.2 H.sub.5                                                                         2,4-Dichlorophenyl                                             101  C.sub.2 H.sub.5                                                                         3,4-Dichlorophenyl                                             102  C.sub.2 H.sub.5                                                                         3,5-Dichlorophenyl                                             103  C.sub.2 H.sub.5                                                                         2,4,6-Trichlorophenyl                                          104  C.sub.2 H.sub.5                                                                         2-Chloro-4-fluorophenyl                                        105  C.sub.2 H.sub.5                                                                         4-Chloro-2-fluorophenyl                                        106  C.sub.2 H.sub.5                                                                         4-Bromophenyl                                                  107  C.sub.2 H.sub.5                                                                         Benzyl                                                         108  C.sub.2 H.sub.5                                                                         2-Methylbenzyl                                                 109  C.sub.2 H.sub.5                                                                         4-Methylbenzyl                                                 110  C.sub.2 H.sub.5                                                                         2,4-Dimethylbenzyl                                             111  C.sub.2 H.sub.5                                                                         2-Fluorobenzyl                                                 112  C.sub.2 H.sub.5                                                                         3-Fluorobenzyl                                                 113  C.sub.2 H.sub.5                                                                         4-Fluorobenzyl                                                 114  C.sub.2 H.sub.5                                                                         2-Chlorobenzyl                                                 115  C.sub.2 H.sub.5                                                                         3-Chlorobenzyl                                                 116  C.sub.2 H.sub.5                                                                         4-Chlorobenzyl                                                 117  C.sub.2 H.sub.5                                                                         2,4-Dichlorobenzyl                                             118  C.sub.2 H.sub.5                                                                         2-Chloro-4-fluorobenzyl                                        119  C.sub.2 H.sub.5                                                                         2-Pyridyl                                                      120  C.sub.2 H.sub.5                                                                         3-Pyridyl                                                      121  C.sub.2 H.sub.5                                                                         4-Pyridyl                                                      122  C.sub.2 H.sub.5                                                                         5-Methyl-2-pyridyl                                             123  C.sub.2 H.sub.5                                                                         6-Methyl-2-pyridyl                                             124  C.sub.2 H.sub.5                                                                         6-Chloro-3-pyridyl                                             125  C.sub.2 H.sub.5                                                                         5-Pyrimidinyl                                                  126  C.sub.2 H.sub.5                                                                         2-Pyrazinyl                                                    127  C.sub.2 H.sub.5                                                                         2-Thienyl                                                      128  C.sub.2 H.sub.5                                                                         3-Thienyl                                                      129  C.sub.2 H.sub.5                                                                         2-Furyl                                                        130  C.sub.2 H.sub.5                                                                         3-Furyl                                                        131  n-C.sub.3 H.sub.7                                                                       Phenyl       3217, 3083, 3060, 2958, 2930, 2870, 1452,                                     1027, 701                                         132  n-C.sub.3 H.sub.7                                                                       2-Methylphenyl                                                                             3218, 2958, 2929, 2870, 1478, 1462, 1413,                                     1028, 744, 713                                    133  n-C.sub.3 H.sub.7                                                                       3-Methylphenyl                                                 134  n-C.sub.3 H.sub.7                                                                       4-Methylphenyl                                                                             3219, 3023, 2958, 2928, 2869, 1454, 1413,                                     1043, 819, 713                                    135  n-C.sub.3 H.sub.7                                                                       2,4-Dimethylphenyl                                                                         3223, 2958, 2927, 2870, 1475, 1414, 1028,                                     713                                               136  n-C.sub.3 H.sub.7                                                                       2,6-Dimethylphenyl                                                                         3220, 2959, 2930, 2871, 1468, 1413, 1268,                                     1047, 1028, 771, 713                              137  n-C.sub.3 H.sub.7                                                                       2,4,6-Trimethylphenyl                                                                      3221, 2958, 2928, 2870, 1477, 1464, 1045,                                     1028, 851, 714                                    138  n-C.sub.3 H.sub.7                                                                       4-Ethylphenyl                                                  139  n-C.sub.3 H.sub.7                                                                       4-Isopropylphenyl                                              140  n-C.sub.3 H.sub.7                                                                       4-tert-Butylphenyl                                             141  n-C.sub.3 H.sub.7                                                                       1-Naphthyl                                                     142  n-C.sub.3 H.sub. 7                                                                      2-Naphthyl                                                     143  n-C.sub.3 H.sub.7                                                                       4-Biphenyl   3200, 3027, 2958, 2930, 2869, 1486, 1044,                                     767, 746, 713, 693                                144  n-C.sub.3 H.sub.7                                                                       4-(2'-Chlorobiphenyl)                                          145  n-C.sub.3 H.sub.7                                                                       4-(4'-Chlorobiphenyl)                                          146  n-C.sub.3 H.sub.7                                                                       2-Methoxyphenyl                                                147  n-C.sub.3 H.sub.7                                                                       3-Methoxyphenyl                                                148  n-C.sub.3 H.sub.7                                                                       4-Methoxyphenyl                                                149  n-C.sub.3 H.sub.7                                                                       3,4-Dimethoxyphenyl                                            150  n-C.sub.3 H.sub.7                                                                       3,4,5-Trimethoxyphenyl                                         151  n-C.sub.3 H.sub.7                                                                       4-tert-Butoxyphenyl                                            152  n-C.sub.3 H.sub.7                                                                       2-Trifluoromethylphenyl                                        153  n-C.sub.3 H.sub.7                                                                       3-Trifluoromethylphenyl                                        154  n-C.sub.3 H.sub.7                                                                       4-Trifluoromethylphenyl                                        155  n-C.sub.3 H.sub.7                                                                       4-Difluoromethoxyphenyl                                        156  n-C.sub.3 H.sub.7                                                                       4-Trifluoromethoxyphenyl                                       157  n-C.sub.3 H.sub.7                                                                       4-Tetrafluoroethoxyphenyl                                      158  n-C.sub.3 H.sub.7                                                                       2-Fluorophenyl                                                 159  n-C.sub.3 H.sub.7                                                                       3-Fluorophenyl                                                 160  n-C.sub.3 H.sub.7                                                                       4-Fluorophenyl                                                                             2959, 2871, 1602, 1506, 1221, 1155, 1027,                                     838, 712                                          161  n-C.sub.3 H.sub.7                                                                       2,4-Difluorophenyl                                             162  n-C.sub.3 H.sub.7                                                                       2-Chlorophenyl                                                 163  n-C.sub.3 H.sub.7                                                                       3-Chlorophenyl                                                 164  n-C.sub.3 H.sub.7                                                                       4-Chlorophenyl                                                                             3203, 2959, 2930, 2870, 1487, 1412, 1090,                                     1014, 828, 712                                    165  n-C.sub.3 H.sub.7                                                                       2,4-Dichlorophenyl                                                                         mp. 166-167° C. (HCl-salt)                 166  n-C.sub.3 H.sub.7                                                                       3,4-Dichlorophenyl                                             167  n-C.sub.3 H.sub.7                                                                       3,5-Dichlorophenyl                                             168  n-C.sub.3 H.sub.7                                                                       2,4,6-Trichlorophenyl                                          169  n-C.sub.3 H.sub.7                                                                       2-Chloro-4-fluorophenyl                                        170  n-C.sub.3 H.sub.7                                                                       4-Chloro-2-fluorophenyl                                        171  n-C.sub.3 H.sub.7                                                                       4-Bromophenyl                                                  172  n-C.sub.3 H.sub.7                                                                       Benzyl                                                         173  n-C.sub.3 H.sub.7                                                                       2-Methylbenzyl                                                 174  n-C.sub.3 H.sub.7                                                                       4-Methylbenzyl                                                 175  n-C.sub.3 H.sub.7                                                                       2,4-Dimethylbenzyl                                             176  n-C.sub.3 H.sub.7                                                                       2-Fluorobenzyl                                                 177  n-C.sub.3 H.sub.7                                                                       3-Fluorobenzyl                                                 178  n-C.sub.3 H.sub.7                                                                       4-Fluorobenzyl                                                 179  n-C.sub.3 H.sub.7                                                                       2-Chlorobenzyl                                                 180  n-C.sub.3 H.sub.7                                                                       3-Chlorobenzyl                                                 181  n-C.sub.3 H.sub.7                                                                       4-Chlorobenzyl                                                 182  n-C.sub.3 H.sub.7                                                                       2,4-Dichlorobenzyl                                             183  n-C.sub.3 H.sub.7                                                                       2-Chloro-4-fluorobenzyl                                        184  n-C.sub.3 H.sub.7                                                                       2-Pyridyl                                                      185  n-C.sub.3 H.sub.7                                                                       3-Pyridyl                                                      186  n-C.sub.3 H.sub.7                                                                       4-Pyridyl                                                      187  n-C.sub.3 H.sub.7                                                                       5-Methyl-2-pyridyl                                             188  n-C.sub.3 H.sub.7                                                                       6-Methyl-2-pyridyl                                             189  n-C.sub.3 H.sub.7                                                                       6-Chloro-3-pyridyl                                             190  n-C.sub.3 H.sub.7                                                                       5-Pyrimidinyl                                                  191  n-C.sub.3 H.sub.7                                                                       2-Pyrazinyl                                                    192  n-C.sub.3 H.sub.7                                                                       2-Thienyl                                                      193  n-C.sub.3 H.sub.7                                                                       3-Thienyl                                                      194  n-C.sub.3 H.sub.7                                                                       2-Furyl                                                        195  n-C.sub.3 H.sub.7                                                                       3-Furyl                                                        196  iso-C.sub.3 H.sub.7                                                                     Phenyl                                                         197  iso-C.sub.3 H.sub.7                                                                     2-Methylphenyl                                                 198  iso-C.sub.3 H.sub.7                                                                     3-Methylphenyl                                                 199  iso-C.sub.3 H.sub.7                                                                     4-Methylphenyl                                                 200  iso-C.sub.3 H.sub.7                                                                     2,4-Dimethylphenyl                                             201  iso-C.sub.3 H.sub.7                                                                     2,6-Dimethylphenyl                                             202  iso-C.sub.3 H.sub.7                                                                     2,4,6-Trimethylphenyl                                          203  iso-C.sub.3 H.sub.7                                                                     4-Ethylphenyl                                                  204  iso-C.sub.3 H.sub.7                                                                     4-Isopropylphenyl                                              205  iso-C.sub.3 H.sub.7                                                                     4-tert-Butylphenyl                                             206  iso-C.sub.3 H.sub.7                                                                     1-Naphthyl                                                     207  iso-C.sub.3 H.sub.7                                                                     2-Naphthyl                                                     208  iso-C.sub.3 H.sub.7                                                                     4-Biphenyl                                                     209  iso-C.sub.3 H.sub.7                                                                     4-(2'-Chlorobiphenyl)                                          210  iso-C.sub.3 H.sub.7                                                                     4-(4'-Chlorobiphenyl)                                          211  iso-C.sub.3 H.sub.7                                                                     2-Methoxyphenyl                                                212  iso-C.sub.3 H.sub.7                                                                     3-Methoxyphenyl                                                213  iso-C.sub.3 H.sub.7                                                                     4-Methoxyphenyl                                                214  iso-C.sub.3 H.sub.7                                                                     3,4-Dimethoxyphenyl                                            215  iso-C.sub.3 H.sub.7                                                                     3,4,5-Trimethoxyphenyl                                         216  iso-C.sub.3 H.sub.7                                                                     4-tert-Butoxyphenyl                                            217  iso-C.sub.3 H.sub.7                                                                     2-Trifluoromethylphenyl                                        218  iso-C.sub.3 H.sub.7                                                                     3-Trifluoromethylphenyl                                        219  iso-C.sub.3 H.sub.7                                                                     4-Trifluoromethylphenyl                                        220  iso-C.sub.3 H.sub.7                                                                     4-Difluoromethoxyphenyl                                        221  iso-C.sub.3 H.sub.7                                                                     4-Trifluoromethoxyphenyl                                       222  iso-C.sub.3 H.sub.7                                                                     4-Tetrafluoroethoxyphenyl                                      223  iso-C.sub.3 H.sub.7                                                                     2-Fluorophenyl                                                 224  iso-C.sub.3 H.sub.7                                                                     3-Fluorophenyl                                                 225  iso-C.sub.3 H.sub.7                                                                     4-Fluorophenyl                                                 226  iso-C.sub.3 H.sub.7                                                                     2,4-Difluorophenyl                                             227  iso-C.sub.3 H.sub.7                                                                     2-Chlorophenyl                                                 228  iso-C.sub.3 H.sub.7                                                                     3-Chlorophenyl                                                 229  iso-C.sub.3 H.sub.7                                                                     4-Chlorophenyl                                                 230  iso-C.sub.3 H.sub.7                                                                     2,4-Dichlorophenyl                                             231  iso-C.sub.3 H.sub.7                                                                     3,4-Dichlorophenyl                                             232  iso-C.sub.3 H.sub.7                                                                     3,5-Dichlorophenyl                                             233  iso-C.sub.3 H.sub.7                                                                     2,4,6-Trichlorophenyl                                          234  iso-C.sub.3 H.sub.7                                                                     2-Chloro-4-fluorophenyl                                        235  iso-C.sub.3 H.sub.7                                                                     4-Chloro-2-fluorophenyl                                        236  iso-C.sub.3 H.sub.7                                                                     4-Bromophenyl                                                  237  iso-C.sub.3 H.sub.7                                                                     Benzyl                                                         238  iso-C.sub.3 H.sub.7                                                                     2-Methylbenzyl                                                 239  iso-C.sub.3 H.sub.7                                                                     4-Methylbenzyl                                                 240  iso-C.sub.3 H.sub.7                                                                     2,4-Dimethylbenzyl                                             241  iso-C.sub.3 H.sub.7                                                                     2-Fluorobenzyl                                                 242  iso-C.sub.3 H.sub.7                                                                     3-Fluorobenzyl                                                 243  iso-C.sub.3 H.sub.7                                                                     4-Fluorobenzyl                                                 244  iso-C.sub.3 H.sub.7                                                                     2-Chlorobenzyl                                                 245  iso-C.sub.3 H.sub.7                                                                     3-Chlorobenzyl                                                 246  iso-C.sub.3 H.sub.7                                                                     4-Chlorobenzyl                                                 247  iso-C.sub.3 H.sub.7                                                                     2,4-Dichlorobenzyl                                             248  iso-C.sub.3 H.sub.7                                                                     2-Chloro-4-fluorobenzyl                                        249  iso-C.sub.3 H.sub.7                                                                     2-Pyridyl                                                      250  iso-C.sub.3 H.sub.7                                                                     3-Pyridyl                                                      251  iso-C.sub.3 H.sub.7                                                                     4-Pyridyl                                                      252  iso-C.sub.3 H.sub.7                                                                     5-Methyl-2-pyridyl                                             253  iso-C.sub.3 H.sub.7                                                                     6-Methyl-2-pyridyl                                             254  iso-C.sub.3 H.sub.7                                                                     6-Chloro-3-pyridyl                                             255  iso-C.sub.3 H.sub.7                                                                     5-Pyrimidinyl                                                  256  iso-C.sub.3 H.sub.7                                                                     2-Pyrazinyl                                                    257  iso-C.sub.3 H.sub.7                                                                     2-Thienyl                                                      258  iso-C.sub.3 H.sub.7                                                                     3-Thienyl                                                      259  iso-C.sub.3 H.sub.7                                                                     2-Furyl                                                        260  iso-C.sub.3 H.sub.7                                                                     3-Furyl                                                        261  n-C.sub.4 H.sub.9                                                                       Phenyl       3208, 3028, 2956, 2931, 2870, 1453, 1413,                                     1025, 702                                         262  n-C.sub.4 H.sub.9                                                                       2-Methylphenyl                                                                             3234, 2955, 2929, 2870, 1478, 1461, 1027,                                     753, 713                                          263  n-C.sub.4 H.sub.9                                                                       3-Methylphenyl                                                 264  n-C.sub.4 H.sub.9                                                                       4-Methylphenyl                                                                             3225, 2956, 2929, 2870, 1466, 1458, 1413,                                     1028, 820, 714                                    265  n-C.sub.4 H.sub.9                                                                       2,4-Dimethylphenyl                                                                         3226, 3031, 2956, 2928, 2870, 1476, 1458,                                     1413, 1027, 713                                   266  n-C.sub.4 H.sub.9                                                                       2,6-Dimethylphenyl                                             267  n-C.sub.4 H.sub.9                                                                       2,4,6-Trimethylphenyl                                          268  n-C.sub.4 H.sub.9                                                                       4-Ethylphenyl                                                  269  n-C.sub.4 H.sub.9                                                                       4-Isopropylphenyl                                              270  n-C.sub.4 H.sub.9                                                                       4-tert-Butylphenyl                                             271  n-C.sub.4 H.sub.9                                                                       1-Naphthyl                                                     272  n-C.sub.4 H.sub.9                                                                       2-Naphthyl                                                     273  n-C.sub.4 H.sub.9                                                                       4-Biphenyl   .sup.1 H-NMR(E-Isomer) δ = 6.80(CCH)                                    5.38(CHOH)                                        274  n-C.sub.4 H.sub.9                                                                       4-(2'-Chlorobiphenyl)                                          275  n-C.sub.4 H.sub.9                                                                       4-(4'-Chlorobiphenyl)                                          276  n-C.sub.4 H.sub.9                                                                       2-Methoxyphenyl                                                277  n-C.sub.4 H.sub.9                                                                       3-Methoxyphenyl                                                278  n-C.sub.4 H.sub.9                                                                       4-Methoxyphenyl                                                279  n-C.sub.4 H.sub.9                                                                       3,4-Dimethoxyphenyl                                            280  n-C.sub.4 H.sub.9                                                                       3,4,5-Trimethoxyphenyl                                         281  n-C.sub.4 H.sub.9                                                                       4-tert-Butoxyphenyl                                            282  n-C.sub.4 H.sub.9                                                                       2-Trifluoromethylphenyl                                        283  n-C.sub.4 H.sub.9                                                                       3-Trifluoromethylphenyl                                        284  n-C.sub.4 H.sub.9                                                                       4-Trifluoromethylphenyl                                        285  n-C.sub.4 H.sub.9                                                                       4-Difluoromethoxyphenyl                                        286  n-C.sub.4 H.sub.9                                                                       4-Trifluoromethoxyphenyl                                       287  n-C.sub.4 H.sub.9                                                                       4-Tetrafluoroethoxyphenyl                                      288  n-C.sub.4 H.sub.9                                                                       2-Fluorophenyl                                                 289  n-C.sub.4 H.sub.9                                                                       3-Fluorophenyl                                                 290  n-C.sub.4 H.sub.9                                                                       4-Fluorophenyl                                                                             3200, 2957, 2931, 2870, 1603, 1507, 1222,                                     1155, 1028, 838, 713                              291  n-C.sub.4 H.sub.9                                                                       2,4-Difluorophenyl                                             292  n-C.sub.4 H.sub.9                                                                       2-Chlorophenyl                                                 293  n-C.sub.4 H.sub.9                                                                       3-Chlorophenyl                                                 294  n-C.sub.4 H.sub.9                                                                       4-Chlorophenyl                                                                             3343, 2930, 2869, 1538, 1488, 1089, 1015,                                     842, 802, 685                                     295  n-C.sub.4 H.sub.9                                                                       2,4-Dichlorophenyl                                                                         .sup.1 H-NMR(E-Isomer) δ = 6.58(CCH),                                   5.70(CHOH)                                        296  n-C.sub.4 H.sub.9                                                                       3,4-Dichlorophenyl                                             297  n-C.sub.4 H.sub.9                                                                       3,5-Dichlorophenyl                                             298  n-C.sub.4 H.sub.9                                                                       2,4,6-Trichlorophenyl                                          299  n-C.sub.4 H.sub.9                                                                       2-Chloro-4-fluorophenyl                                        300  n-C.sub.4 H.sub.9                                                                       4-Chloro-2-fluorophenyl                                        301  n-C.sub.4 H.sub.9                                                                       4-Bromophenyl                                                  302  n-C.sub.4 H.sub.9                                                                       Benzyl                                                         303  n-C.sub.4 H.sub.9                                                                       2-Methylbenzyl                                                 304  n-C.sub.4 H.sub.9                                                                       4-Methylbenzyl                                                 305  n-C.sub.4 H.sub.9                                                                       2,4-Dimethylbenzyl                                             306  n-C.sub.4 H.sub.9                                                                       2-Fluorobenzyl                                                 307  n-C.sub.4 H.sub.9                                                                       3-Fluorobenzyl                                                 308  n-C.sub.4 H.sub.9                                                                       4-Fluorobenzyl                                                 309  n-C.sub.4 H.sub.9                                                                       2-Chlorobenzyl                                                 310  n-C.sub.4 H.sub.9                                                                       3-Chlorobenzyl                                                 311  n-C.sub.4 H.sub.9                                                                       4-Chlorobenzyl                                                 312  n-C.sub.4 H.sub.9                                                                       2,4-Dichlorobenzyl                                             313  n-C.sub.4 H.sub.9                                                                       2-Chloro-4-fluorobenzyl                                        314  n-C.sub.4 H.sub.9                                                                       2-Pyridyl                                                      315  n-C.sub.4 H.sub.9                                                                       3-Pyridyl    mp. 160-162° C.(×2 HCl)              316  n-C.sub.4 H.sub.9                                                                       4-Pyridyl                                                      317  n-C.sub.4 H.sub.9                                                                       5-Methyl-2-pyridyl                                             318  n-C.sub.4 H.sub.9                                                                       6-Methyl-2-pyridyl                                             319  n-C.sub.4 H.sub.9                                                                       6-Chloro-3-pyridyl                                             320  n-C.sub.4 H.sub.9                                                                       5-Pyrimidinyl                                                  321  n-C.sub.4 H.sub.9                                                                       2-Pyrazinyl                                                    322  n-C.sub.4 H.sub.9                                                                       2-Thienyl                                                      323  n-C.sub.4 H.sub.9                                                                       3-Thienyl                                                      324  n-C.sub.4 H.sub.9                                                                       2-Furyl                                                        325  n-C.sub.4 H.sub.9                                                                       3-Furyl                                                        326  tert.-C.sub.4 H.sub.9                                                                   Phenyl       3206, 2963, 2907, 2871, 1478, 1448, 1366,                                     1045, 1029, 705                                   327  tert.-C.sub.4 H.sub.9                                                                   2-Methylphenyl                                                 328  tert.-C.sub.4 H.sub.9                                                                   3-Methylphenyl                                                 329  tert.-C.sub.4 H.sub.9                                                                   4-Methylphenyl                                                 330  tert.-C.sub.4 H.sub.9                                                                   2,4-Dimethylphenyl                                             331  tert.-C.sub.4 H.sub.9                                                                   2,6-Dimethylphenyl                                             332  tert.-C.sub.4 H.sub.9                                                                   2,4,6-Trimethylphenyl                                          333  tert.-C.sub.4 H.sub.9                                                                   4-Ethylphenyl                                                  334  tert.-C.sub.4 H.sub.9                                                                   4-Isopropylphenyl                                              335  tert.-C.sub.4 H.sub.9                                                                   4-tert-Butylphenyl                                             336  tert.-C.sub.4 H.sub.9                                                                   1-Naphthyl                                                     337  tert.-C.sub.4 H.sub.9                                                                   2-Naphthyl                                                     338  tert.-C.sub.4 H.sub.9                                                                   4-Biphenyl                                                     339  tert.-C.sub.4 H.sub.9                                                                   4-(2'-Chlorobiphenyl)                                          340  tert.-C.sub.4 H.sub.9                                                                   4-(4'-Chlorobiphenyl)                                          341  tert.-C.sub.4 H.sub.9                                                                   2-Methoxyphenyl                                                342  tert.-C.sub.4 H.sub.9                                                                   3-Methoxyphenyl                                                343  tert.-C.sub.4 H.sub.9                                                                   4-Methoxyphenyl                                                344  tert.-C.sub.4 H.sub.9                                                                   3,4-Dimethoxyphenyl                                            345  tert.-C.sub.4 H.sub.9                                                                   3,4,5-Trimethoxyphenyl                                         346  tert.-C.sub.4 H.sub.9                                                                   4-tert-Butoxyphenyl                                            347  tert.-C.sub.4 H.sub.9                                                                   2-Trifluoromethylphenyl                                        348  tert.-C.sub.4 H.sub.9                                                                   3-Trifluoromethylphenyl                                        349  tert.-C.sub.4 H.sub.9                                                                   4-Trifluoromethylphenyl                                        350  tert.-C.sub.4 H.sub.9                                                                   4-Difluoromethoxyphenyl                                        351  tert.-C.sub.4 H.sub.9                                                                   4-Trifluoromethoxyphenyl                                       352  tert.-C.sub.4 H.sub.9                                                                   4-Tetrafluoroethoxyphenyl                                      353  tert.-C.sub.4 H.sub.9                                                                   2-Fluorophenyl                                                 354  tert.-C.sub.4 H.sub.9                                                                   3-Fluorophenyl                                                 355  tert.-C.sub.4 H.sub.9                                                                   4-Fluorophenyl                                                                             3223, 1506, 1485, 1219, 1028, 825, 812,                                       714                                               356  tert.-C.sub.4 H.sub.9                                                                   2,4-Difluorophenyl                                             357  tert.-C.sub.4 H.sub.9                                                                   2-Chlorophenyl                                                 358  tert.-C.sub.4 H.sub.9                                                                   3-Chlorophenyl                                                 359  tert.-C.sub.4 H.sub.9                                                                   4-Chlorophenyl                                                                             3180, 2970, 2962, 1483, 1479, 1394, 1065,                                     1027, 1003, 804, 750, 714                         360  tert.-C.sub.4 H.sub.9                                                                   2,4-Dichlorophenyl                                                                         3200, 2967, 2908, 2871, 1467, 1381, 1091,                                     1066, 1037, 713                                   361  tert.-C.sub.4 H.sub.9                                                                   3,4-Dichlorophenyl                                             362  tert.-C.sub.4 H.sub.9                                                                   3,5-Dichlorophenyl                                             363  tert.-C.sub.4 H.sub.9                                                                   2,4,6-Trichlorophenyl                                          364  tert.-C.sub.4 H.sub.9                                                                   2-Chloro-4-fluorophenyl                                        365  tert.-C.sub.4 H.sub.9                                                                   4-Chloro-2-fluorophenyl                                        366  tert.-C.sub.4 H.sub.9                                                                   4-Bromophenyl                                                  367  tert.-C.sub.4 H.sub.9                                                                   Benzyl                                                         368  tert.-C.sub.4 H.sub.9                                                                   2-Methylbenzyl                                                 369  tert.-C.sub.4 H.sub.9                                                                   4-Methylbenzyl                                                 370  tert.-C.sub.4 H.sub.9                                                                   2,4-Dimethylbenzyl                                             371  tert.-C.sub.4 H.sub.9                                                                   2-Fluorobenzyl                                                 372  tert.-C.sub.4 H.sub.9                                                                   3-Fluorobenzyl                                                 373  tert.-C.sub.4 H.sub.9                                                                   4-Fluorobenzyl                                                 374  tert.-C.sub.4 H.sub.9                                                                   2-Chlorobenzyl                                                 375  tert.-C.sub.4 H.sub.9                                                                   3-Chlorobenzyl                                                 376  tert.-C.sub.4 H.sub.9                                                                   4-Chlorobenzyl                                                 377  tert.-C.sub.4 H.sub.9                                                                   2,4-Dichlorobenzyl                                             378  tert.-C.sub.4 H.sub.9                                                                   2-Chloro-4-fluorobenzyl                                        379  tert.-C.sub.4 H.sub.9                                                                   2-Pyridyl                                                      380  tert.-C.sub.4 H.sub.9                                                                   3-Pyridyl                                                      381  tert.-C.sub.4 H.sub.9                                                                   4-Pyridyl                                                      382  tert.-C.sub.4 H.sub.9                                                                   5-Methyl-2-pyridyl                                             383  tert.-C.sub.4 H.sub.9                                                                   6-Methyl-2-pyridyl                                             384  tert.-C.sub.4 H.sub.9                                                                   6-Chloro-3-pyridyl                                             385  tert.-C.sub.4 H.sub.9                                                                   5-Pyrimidinyl                                                  386  tert.-C.sub.4 H.sub.9                                                                   2-Pyrazinyl                                                    387  tert.-C.sub.4 H.sub.9                                                                   2-Thienyl                                                      388  tert.-C.sub.4 H.sub.9                                                                   3-Thienyl                                                      389  tert.-C.sub.4 H.sub.9                                                                   2-Furyl                                                        390  tert.-C.sub.4 H.sub.9                                                                   3-Furyl                                                        391  n-C.sub.5 H.sub.11                                                                      Phenyl       3240, 2954, 2927, 2869, 1453, 1414, 1026,                                     701                                               392  n-C.sub.5 H.sub.11                                                                      2-Methylphenyl                                                 393  n-C.sub.5 H.sub.11                                                                      3-Methylphenyl                                                 394  n-C.sub.5 H.sub.11                                                                      4-Methylphenyl                                                 395  n-C.sub.5 H.sub.11                                                                      2,4-Dimethylphenyl                                                                         3240, 2954, 2927, 2927, 2869, 1466, 1457,                                     1414, 1028, 713                                   396  n-C.sub.5 H.sub.11                                                                      2,6-Dimethylphenyl                                             397  n-C.sub.5 H.sub.11                                                                      2,4,6-Trimethylphenyl                                          398  n-C.sub.5 H.sub.11                                                                      4-Ethylphenyl                                                  399  n-C.sub.5 H.sub.11                                                                      4-Isopropylphenyl                                              400  n-C.sub.5 H.sub.11                                                                      4-tert-Butylphenyl                                             401  n-C.sub.5 H.sub.11                                                                      1-Naphthyl                                                     402  n-C.sub.5 H.sub.11                                                                      2-Naphthyl                                                     403  n-C.sub. 5 H.sub.11                                                                     4-Biphenyl                                                     404  n-C.sub.5 H.sub.11                                                                      4-(2'-Chlorobiphenyl)                                          405  n-C.sub.5 H.sub.11                                                                      4-(4'-Chlorobiphenyl)                                          406  n-C.sub.5 H.sub.11                                                                      2-Methoxyphenyl                                                407  n-C.sub.5 H.sub.11                                                                      3-Methoxyphenyl                                                408  n-C.sub.5 H.sub.11                                                                      4-Methoxyphenyl                                                409  n-C.sub.5 H.sub.11                                                                      3,4-Dimethoxyphenyl                                            410  n-C.sub.5 H.sub.11                                                                      3,4,5-Trimethoxyphenyl                                         411  n-C.sub.5 H.sub.11                                                                      4-tert-Butoxyphenyl                                            412  n-C.sub.5 H.sub.11                                                                      2-Trifluoromethylphenyl                                        413  n-C.sub.5 H.sub.11                                                                      3-Trifluoromethylphenyl                                        414  n-C.sub.5 H.sub.11                                                                      4-Trifluoromethylphenyl                                        415  n-C.sub.5 H.sub.11                                                                      4-Difluoromethoxyphenyl                                        416  n-C.sub.5 H.sub.11                                                                      4-Trifluoromethoxyphenyl                                       417  n-C.sub.5 H.sub.11                                                                      4-Tetrafluoroethoxyphenyl                                      418  n-C.sub.5 H.sub.11                                                                      2-Fluorophenyl                                                 419  n-C.sub.5 H.sub.11                                                                      3-Fluorophenyl                                                 420  n-C.sub.5 H.sub.11                                                                      4-Fluorophenyl                                                                             3200, 2955, 2930, 2869, 1603, 1507, 1227                                      1155, 838, 713                                    421  n-C.sub.5 H.sub.11                                                                      2,4-Difluorophenyl                                             422  n-C.sub.5 H.sub.11                                                                      2-Chlorophenyl                                                 423  n-C.sub.5 H.sub.11                                                                      3-Chlorophenyl                                                 424  n-C.sub.5 H.sub.11                                                                      4-Chlorophenyl                                                                             3208, 2955, 2929, 2869, 1488, 1090, 1015,                                     827, 712                                          425  n-C.sub.5 H.sub.11                                                                      2,4-Dichlorophenyl                                                                         mp. 153-155° C. (×HCl)               426  n-C.sub.5 H.sub.11                                                                      3,4-Dichlorophenyl                                             427  n-C.sub.5 H.sub.11                                                                      3,5-Dichlorophenyl                                             428  n-C.sub.5 H.sub.11                                                                      2,4,6-Trichlorophenyl                                          429  n-C.sub.5 H.sub.11                                                                      2-Chloro-4-fluorophenyl                                        430  n-C.sub.5 H.sub.11                                                                      4-Chloro-2-fluorophenyl                                        431  n-C.sub.5 H.sub.11                                                                      4-Bromophenyl                                                  432  n-C.sub.5 H.sub.11                                                                      Benzyl                                                         433  n-C.sub.5 H.sub.11                                                                      2-Methylbenzyl                                                 434  n-C.sub.5 H.sub.11                                                                      4-Methylbenzyl                                                 435  n-C.sub.5 H.sub.11                                                                      2,4-Dimethylbenzyl                                             436  n-C.sub.5 H.sub.11                                                                      2-Fluorobenzyl                                                 437  n-C.sub.5 H.sub.11                                                                      3-Fluorobenzyl                                                 438  n-C.sub.5 H.sub.11                                                                      4-Fluorobenzyl                                                 439  n-C.sub.5 H.sub.11                                                                      2-Chlorobenzyl                                                 440  n-C.sub.5 H.sub.11                                                                      3-Chlorobenzyl                                                 441  n-C.sub.5 H.sub.11                                                                      4-Chlorobenzyl                                                 442  n-C.sub.5 H.sub.11                                                                      2,4-Dichlorobenzyl                                             443  n-C.sub.5 H.sub.11                                                                      2-Chloro-4-fluorobenzyl                                        444  n-C.sub.5 H.sub.11                                                                      2-Pyridyl                                                      445  n-C.sub.5 H.sub.11                                                                      3-Pyridyl                                                      446  n-C.sub.5 H.sub.11                                                                      4-Pyridyl                                                      447  n-C.sub.5 H.sub.11                                                                      5-Methyl-2-pyridyl                                             448  n-C.sub.5 H.sub.11                                                                      6-Methyl-2-pyridyl                                             449  n-C.sub.5 H.sub.11                                                                      6-Chloro-3-pyridyl                                             450  n-C.sub.5 H.sub.11                                                                      5-Pyrimidinyl                                                  451  n-C.sub.5 H.sub.11                                                                      2-Pyrazinyl                                                    452  n-C.sub.5 H.sub.11                                                                      2-Thienyl                                                      453  n-C.sub.5 H.sub.11                                                                      3-Thienyl                                                      454  n-C.sub.5 H.sub.11                                                                      2-Furyl                                                        455  n-C.sub.5 H.sub.11                                                                      3-Furyl                                                        456  neo-C.sub.5 H.sub.11                                                                    Phenyl       .sup.1 H-NMR: E-Isomer: δ = 7.05                                        (CCH),                                                                        5.38 (C .sub.-- HOH), 2.58, 1.63, 0.80                                        (CH.sub.2 C(CH.sub.3).sub.3). Z-Isomer:                                       δ = 6.62                                                                (CC .sub.-- H), 5.70(C .sub.-- HOH), 2.10,                                    1.98, 0.98                                                                    (CH.sub.2 C(CH.sub.3).sub.3).                     457  neo-C.sub.5 H.sub.11                                                                    2-Methylphenyl                                                                             2952, 2864, 1476, 1464, 1364, 1046, 1028,                                     760, 728, 715                                     458  neo-C.sub.5 H.sub.11                                                                    3-Methylphenyl                                                 459  neo-C.sub.5 H.sub.11                                                                    4-Methylphenyl                                                                             mp. 154-156° C. (×HCl)               460  neo-C.sub.5 H.sub.11                                                                    2,4-Dimethylphenyl                                                                         3227, 2951, 2864, 1476, 1467, 1412, 1363,                                     1045, 1028, 715                                   461  neo-C.sub.5 H.sub.11                                                                    2,6-Dimethylphenyl                                             462  neo-C.sub.5 H.sub.11                                                                    2,4,6-Trimethylphenyl                                          463  neo-C.sub.5 H.sub.11                                                                    4-Ethylphenyl                                                  464  neo-C.sub.5 H.sub.11                                                                    4-Isopropylphenyl                                              465  neo-C.sub.5 H.sub.11                                                                    4-tert-Butylphenyl                                             466  neo-C.sub.5 H.sub.11                                                                    1-Naphthyl                                                     467  neo-C.sub.5 H.sub.11                                                                    2-Naphthyl                                                     468  neo-C.sub.5 H.sub.11                                                                    4-Biphenyl                                                     469  neo-C.sub.5 H.sub.11                                                                    4-(2'-Chlorobiphenyl)                                          470  neo-C.sub.5 H.sub.11                                                                    4-(4'-Chlorobiphenyl)                                          471  neo-C.sub.5 H.sub.11                                                                    2-Methoxyphenyl                                                472  neo-C.sub.5 H.sub.11                                                                    3-Methoxyphenyl                                                473  neo-C.sub.5 H.sub.11                                                                    4-Methoxyphenyl                                                474  neo-C.sub.5 H.sub.11                                                                    3,4-Dimethoxyphenyl                                            475  neo-C.sub.5 H.sub.11                                                                    3,4,5-Trimethoxyphenyl                                         476  neo-C.sub.5 H.sub.11                                                                    4-tert-Butoxyphenyl                                            477  neo-C.sub.5 H.sub.11                                                                    2-Trifluoromethylphenyl                                        478  neo-C.sub.5 H.sub.11                                                                    3-Trifluoromethylphenyl                                        479  neo-C.sub.5 H.sub.11                                                                    4-Trifluoromethylphenyl                                        480  neo-C.sub.5 H.sub.11                                                                    4-Difluoromethoxyphenyl                                        481  neo-C.sub.5 H.sub.11                                                                    4-Trifluoromethoxyphenyl                                       482  neo-C.sub.5 H.sub.11                                                                    4-Tetrafluoroethoxyphenyl                                      483  neo-C.sub.5 H.sub.11                                                                    2-Fluorophenyl                                                 484  neo-C.sub.5 H.sub.11                                                                    3-Fluorophenyl                                                 485  neo-C.sub.5 H.sub.11                                                                    4-Fluorophenyl                                                                             .sup.1 H-NMR: E-Isomer: δ = 7.00 (CC                                    .sub.-- H)                                                                    5.38 (C .sub.-- HOH), 0.78 (CMe.sub.3).                                       Z-Isomer: δ = 6.60 (CC .sub.-- H),                                      5.65 (C .sub.-- HOH), 0.97 (CMe.sub.3)            486  neo-C.sub.5 H.sub.11                                                                    2,4-Difluorophenyl                                             487  neo-C.sub.5 H.sub.11                                                                    2-Chlorophenyl                                                 488  neo-C.sub.5 H.sub.11                                                                    3-Chlorophenyl                                                 489  neo-C.sub.5 H.sub.11                                                                    4-Chlorophenyl                                                                             .sup.1 H-NMR: E-Isomer: δ = 7.00 (CC                                    .sub.-- H)                                                                    5.35 (C .sub.-- HOH), 2.55, 1.63, 0.78                                        (CH.sub.2 CMe.sub.3).                                                         Z-Isomer: δ = 6.58 (CC .sub.-- H), 5.62                                 (C .sub.-- HOH),                                                              2.08, 1.95, 0.98 (CH.sub.2 CMe.sub.3)             490  neo-C.sub.5 H.sub.11                                                                    2,4-Dichlorophenyl                                                                         mp. 120° C. (Zers.) (×HCl)           491  neo-C.sub.5 H.sub.11                                                                    3,4-Dichlorophenyl                                             492  neo-C.sub.5 H.sub.11                                                                    3,5-Dichlorophenyl                                             493  neo-C.sub.5 H.sub.11                                                                    2,4,6-Trichlorophenyl                                          494  neo-C.sub.5 H.sub.11                                                                    2-Chloro-4-fluorophenyl                                        495  neo-C.sub.5 H.sub.11                                                                    4-Chloro-2-fluorophenyl                                        496  neo-C.sub.5 H.sub.11                                                                    4-Bromophenyl                                                  497  neo-C.sub.5 H.sub.11                                                                    Benzyl                                                         498  neo-C.sub.5 H.sub.11                                                                    2-Methylbenzyl                                                 499  neo-C.sub.5 H.sub.11                                                                    4-Methylbenzyl                                                 500  neo-C.sub.5 H.sub.11                                                                    2,4-Dimethylbenzyl                                             501  neo-C.sub.5 H.sub.11                                                                    2-Fluorobenzyl                                                 502  neo-C.sub.5 H.sub.11                                                                    3-Fluorobenzyl                                                 503  neo-C.sub.5 H.sub.11                                                                    4-Fluorobenzyl                                                 504  neo-C.sub.5 H.sub.11                                                                    2-Chlorobenzyl                                                 505  neo-C.sub.5 H.sub.11                                                                    3-Chlorobenzyl                                                 506  neo-C.sub.5 H.sub.11                                                                    4-Chlorobenzyl                                                 507  neo-C.sub.5 H.sub.11                                                                    2,4-Dichlorobenzyl                                             508  neo-C.sub.5 H.sub.11                                                                    2-Chloro-4-fluorobenzyl                                        509  neo-C.sub.5 H.sub.11                                                                    2-Pyridyl                                                      510  neo-C.sub.5 H.sub.11                                                                    3-Pyridyl                                                      511  neo-C.sub.5 H.sub.11                                                                    4-Pyridyl                                                      512  neo-C.sub.5 H.sub.11                                                                    5-Methyl-2-pyridyl                                             513  neo-C.sub.5 H.sub.11                                                                    6-Methyl-2-pyridyl                                             514  neo-C.sub.5 H.sub.11                                                                    6-Chloro-3-pyridyl                                             515  neo-C.sub.5 H.sub.11                                                                    5-Pyrimidinyl                                                  516  neo-C.sub.5 H.sub.11                                                                    2-Pyrazinyl                                                    517  neo-C.sub.5 H.sub.11                                                                    2-Thienyl                                                      518  neo-C.sub.5 H.sub.11                                                                    3-Thienyl                                                      519  neo-C.sub.5 H.sub.11                                                                    2-Furyl                                                        520  neo-C.sub.5 H.sub.11                                                                    3-Furyl                                                        521  n-C.sub.6 H.sub.13                                                                      Phenyl       3219, 2954, 2927, 2856, 1467, 1453, 1045,                                     1026, 713, 701                                    522  n-C.sub.6 H.sub.13                                                                      2-Methylphenyl                                                 523  n-C.sub.6 H.sub.13                                                                      3-Methylphenyl                                                 524  n-C.sub.6 H.sub.13                                                                      4-Methylphenyl                                                 525  n-C.sub.6 H.sub.13                                                                      2,4-Dimethylphenyl                                             526  n-C.sub.6 H.sub.13                                                                      2,6-Dimethylphenyl                                             527  n-C.sub.6 H.sub.13                                                                      2,4,6-Trimethylphenyl                                          528  n-C.sub.6 H.sub.13                                                                      4-Ethylphenyl                                                  529  n-C.sub.6 H.sub.13                                                                      4-Isopropylphenyl                                              530  n-C.sub.6 H.sub.13                                                                      4-tert-Butylphenyl                                             531  n-C.sub.6 H.sub.13                                                                      1-Naphthyl                                                     532  n-C.sub.6 H.sub.13                                                                      2-Naphthyl                                                     533  n-C.sub.6 H.sub.13                                                                      4-Biphenyl                                                     534  n-C.sub.6 H.sub.13                                                                      4-(2'-Chlorobiphenyl)                                          535  n-C.sub.6 H.sub.13                                                                      4-(4'-Chlorobiphenyl)                                          536  n-C.sub.6 H.sub.13                                                                      2-Methoxyphenyl                                                537  n-C.sub.6 H.sub.13                                                                      3-Methoxyphenyl                                                538  n-C.sub.6 H.sub.13                                                                      4-Methoxyphenyl                                                539  n-C.sub.6 H.sub.13                                                                      3,4-Dimethoxyphenyl                                            540  n-C.sub.6 H.sub.13                                                                      3,4,5-Trimethoxyphenyl                                         541  n-C.sub.6 H.sub.13                                                                      4-tert-Butoxyphenyl                                            542  n-C.sub.6 H.sub.13                                                                      2-Trifluoromethylphenyl                                        543  n-C.sub.6 H.sub.13                                                                      3-Trifluoromethylphenyl                                        544  n-C.sub.6 H.sub.13                                                                      4-Trifluoromethylphenyl                                        545  n-C.sub.6 H.sub.13                                                                      4-Difluoromethoxyphenyl                                        546  n-C.sub.6 H.sub.13                                                                      4-Trifluoromethoxyphenyl                                       547  n-C.sub.6 H.sub.13                                                                      4-Tetrafluoroethoxyphenyl                                      548  n-C.sub.6 H.sub.13                                                                      2-Fluorophenyl                                                 549  n-C.sub.6 H.sub.13                                                                      3-Fluorophenyl                                                 550  n-C.sub.6 H.sub.13                                                                      4-Fluorophenyl                                                                             3200, 2955, 2929, 2857, 1507, 1222, 1155                                      838, 713                                          551  n-C.sub.6 H.sub.13                                                                      2,4-Difluorophenyl                                             552  n-C.sub.6 H.sub.13                                                                      2-Chlorophenyl                                                 553  n-C.sub.6 H.sub.13                                                                      3-Chlorophenyl                                                 554  n-C.sub.6 H.sub.13                                                                      4-Chlorophenyl                                                                             3200, 2955, 2928, 2869, 2856, 1488, 1091,                                     1051, 829, 712                                    555  n-C.sub.6 H.sub.13                                                                      2,4-Dichlorophenyl                                                                         3260, 2953, 2928, 2856, 1587, 1572, 1560,                                     1468, 1414, 1312, 715                             556  n-C.sub.6 H.sub.13                                                                      3,4-Dichlorophenyl                                             557  n-C.sub.6 H.sub.13                                                                      3,5-Dichlorophenyl                                             558  n-C.sub.6 H.sub.13                                                                      2,4,6-Trichlorophenyl                                          559  n-C.sub.6 H.sub.13                                                                      2-Chloro-4-fluorophenyl                                        560  n-C.sub.6 H.sub.13                                                                      4-Chloro-2-fluorophenyl                                        561  n-C.sub.6 H.sub.13                                                                      4-Bromophenyl                                                  562  n-C.sub.6 H.sub.13                                                                      Benzyl                                                         563  n-C.sub.6 H.sub.13                                                                      2-Methylbenzyl                                                 564  n-C.sub.6 H.sub.13                                                                      4-Methylbenzyl                                                 565  n-C.sub.6 H.sub.13                                                                      2,4-Dimethylbenzyl                                             566  n-C.sub.6 H.sub.13                                                                      2-Fluorobenzyl                                                 567  n-C.sub.6 H.sub.13                                                                      3-Fluorobenzyl                                                 568  n-C.sub.6 H.sub.13                                                                      4-Fluorobenzyl                                                 569  n-C.sub.6 H.sub.13                                                                      2-Chlorobenzyl                                                 570  n-C.sub.6 H.sub.13                                                                      3-Chlorobenzyl                                                 571  n-C.sub.6 H.sub.13                                                                      4-Chlorobenzyl                                                 572  n-C.sub.6 H.sub.13                                                                      2,4-Dichlorobenzyl                                             573  n-C.sub.6 H.sub.13                                                                      2-Chloro-4-fluorobenzyl                                        574  n-C.sub.6 H.sub.13                                                                      2-Pyridyl                                                      575  n-C.sub.6 H.sub.13                                                                      3-Pyridyl                                                      576  n-C.sub.6 H.sub.13                                                                      4-Pyridyl                                                      577  n-C.sub.6 H.sub.13                                                                      5-Methyl-2-pyridyl                                             578  n-C.sub.6 H.sub.13                                                                      6-Methyl-2-pyridyl                                             579  n-C.sub.6 H.sub.13                                                                      6-Chloro-3-pyridyl                                             580  n-C.sub. 6 H.sub.13                                                                     5-Pyrimidinyl                                                  581  n-C.sub.6 H.sub.13                                                                      2-Pyrazinyl                                                    582  n-C.sub.6 H.sub.13                                                                      2-Thienyl                                                      583  n-C.sub.6 H.sub.13                                                                      3-Thienyl                                                      584  n-C.sub.6 H.sub.13                                                                      2-Furyl                                                        585  n-C.sub.6 H.sub.13                                                                      3-Furyl                                                        586  Phenyl    Phenyl       mp. 149° C.                                587  Phenyl    2-Methylphenyl                                                 588  Phenyl    3-Methylphenyl                                                 589  Phenyl    4-Methylphenyl                                                 590  Phenyl    2,4-Dimethylphenyl                                             591  Phenyl    2,6-Dimethylphenyl                                             592  Phenyl    2,4,6-Trimethylphenyl                                          593  Phenyl    4-Ethylphenyl                                                  594  Phenyl    4-Isopropylphenyl                                              595  Phenyl    4-tert-Butylphenyl                                             596  Phenyl    1-Naphthyl                                                     597  Phenyl    2-Naphthyl                                                     598  Phenyl    4-Biphenyl                                                     599  Phenyl    4-(2'-Chlorobiphenyl)                                          600  Phenyl    4-(4'-Chlorobiphenyl)                                          601  Phenyl    2-Methoxyphenyl                                                602  Phenyl    3-Methoxyphenyl                                                603  Phenyl    4-Methoxyphenyl                                                604  Phenyl    3,4-Dimethoxyphenyl                                            605  Phenyl    3,4,5-Trimethoxyphenyl                                         606  Phenyl    4-tert-Butoxyphenyl                                            607  Phenyl    2-Trifluoromethylphenyl                                        608  Phenyl    3-Trifluoromethylphenyl                                        609  Phenyl    4-Trifluoromethylphenyl                                        610  Phenyl    4-Difluoromethoxyphenyl                                        611  Phenyl    4-Trifluoromethoxyphenyl                                       612  Phenyl    4-Tetrafluoroethoxyphenyl                                      613  Phenyl    2-Fluorophenyl                                                 614  Phenyl    3-Fluorophenyl                                                 615  Phenyl    4-Fluorophenyl                                                 616  Phenyl    2,4-Difluorophenyl                                             617  Phenyl    2-Chlorophenyl                                                 618  Phenyl    3-Chlorophenyl                                                 619  Phenyl    4-Chlorophenyl                                                                             mp. 89° C.                                 620  Phenyl    2,4-Dichlorophenyl                                             621  Phenyl    3,4-Dichlorophenyl                                             622  Phenyl    3,5-Dichlorophenyl                                             623  Phenyl    2,4,6-Trichlorophenyl                                          624  Phenyl    2-Chloro-4-fluorophenyl                                        625  Phenyl    4-Chloro-2-fluorophenyl                                        626  Phenyl    4-Bromophenyl                                                  627  Phenyl    Benzyl                                                         628  Phenyl    2-Methylbenzyl                                                 629  Phenyl    4-Methylbenzyl                                                 630  Phenyl    2,4-Dimethylbenzyl                                             631  Phenyl    2-Fluorobenzyl                                                 632  Phenyl    3-Fluorobenzyl                                                 633  Phenyl    4-Fluorobenzyl                                                 634  Phenyl    2-Chlorobenzyl                                                 635  Phenyl    3-Chlorobenzyl                                                 636  Phenyl    4-Chlorobenzyl                                                 637  Phenyl    2,4-Dichlorobenzyl                                             638  Phenyl    2-Chloro-4-fluorobenzyl                                        639  Phenyl    2-Pyridyl                                                      640  Phenyl    3-Pyridyl                                                      641  Phenyl    4-Pyridyl                                                      642  Phenyl    5-Methyl-2-pyridyl                                             643  Phenyl    6-Methyl-2-pyridyl                                             644  Phenyl    6-Chloro-3-pyridyl                                             645  Phenyl    5-Pyrimidinyl                                                  646  Phenyl    2-Pyrazinyl                                                    647  Phenyl    2-Thienyl                                                      648  Phenyl    3-Thienyl                                                      649  Phenyl    2-Furyl                                                        650  Phenyl    3-Furyl                                                        651  4-Fluorophenyl                                                                          Phenyl       mp. 96° C.                                 652  4-Fluorophenyl                                                                          2-Methylphenyl                                                 653  4-Fluorophenyl                                                                          3-Methylphenyl                                                 654  4-Fluorophenyl                                                                          4-Methylphenyl                                                 655  4-Fluorophenyl                                                                          2,4-Dimethylphenyl                                             656  4-Fluorophenyl                                                                          2,6-Dimethylphenyl                                             657  4-Fluorophenyl                                                                          2,4,6-Trimethylphenyl                                          658  4-Fluorophenyl                                                                          4-Ethylphenyl                                                  659  4-Fluorophenyl                                                                          4-Isopropylphenyl                                              660  4-Fluorophenyl                                                                          4-tert-Butylphenyl                                             661  4-Fluorophenyl                                                                          1-Naphthyl                                                     662  4-Fluorophenyl                                                                          2-Naphthyl                                                     663  4-Fluorophenyl                                                                          4-Biphenyl                                                     664  4-Fluorophenyl                                                                          4-(2'-Chlorobiphenyl)                                          665  4-Fluorophenyl                                                                          4-(4'-Chlorobiphenyl)                                          666  4-Fluorophenyl                                                                          2-Methoxyphenyl                                                667  4-Fluorophenyl                                                                          3-Methoxyphenyl                                                668  4-Fluorophenyl                                                                          4-Methoxyphenyl                                                669  4-Fluorophenyl                                                                          3,4-Dimethoxyphenyl                                            670  4-Fluorophenyl                                                                          3,4,5-Trimethoxyphenyl                                         671  4-Fluorophenyl                                                                          4-tert-Butoxyphenyl                                            672  4-Fluorophenyl                                                                          2-Trifluoromethylphenyl                                        673  4-Fluorophenyl                                                                          3-Trifluoromethylphenyl                                        674  4-Fluorophenyl                                                                          4-Trifluoromethylphenyl                                        675  4-Fluorophenyl                                                                          4-Difluoromethoxyphenyl                                        676  4-Fluorophenyl                                                                          4-Trifluoromethoxyphenyl                                       677  4-Fluorophenyl                                                                          4-Tetrafluoroethoxyphenyl                                      678  4-Fluorophenyl                                                                          2-Fluorophenyl                                                 679  4-Fluorophenyl                                                                          3-Fluorophenyl                                                 680  4-Fluorophenyl                                                                          4-Fluorophenyl                                                 681  4-Fluorophenyl                                                                          2,4-Difluorophenyl                                             682  4-Fluorophenyl                                                                          2-Chlorophenyl                                                                             mp. 82-83° C.                              683  4-Fluorophenyl                                                                          3-Chlorophenyl                                                 684  4-Fluorophenyl                                                                          4-Chlorophenyl                                                                             mp. 104° C.                                685  4-Fluorophenyl                                                                          2,4-Dichlorophenyl                                             686  4-Fluorophenyl                                                                          3,4-Dichlorophenyl                                             687  4-Fluorophenyl                                                                          3,5-Dichlorophenyl                                             688  4-Fluorophenyl                                                                          2,4,6-Trichlorophenyl                                          689  4-Fluorophenyl                                                                          2-Chloro-4-fluorophenyl                                        690  4-Fluorophenyl                                                                          4-Chloro-2-fluorophenyl                                        691  4-Fluorophenyl                                                                          4-Bromophenyl                                                  692  4-Fluorophenyl                                                                          Benzyl                                                         693  4-Fluorophenyl                                                                          2-Methylbenzyl                                                 694  4-Fluorophenyl                                                                          4-Methylbenzyl                                                 695  4-Fluorophenyl                                                                          2,4-Dimethylbenzyl                                             696  4-Fluorophenyl                                                                          2-Fluorobenzyl                                                 697  4-Fluorophenyl                                                                          3-Fluorobenzyl                                                 698  4-Fluorophenyl                                                                          4-Fluorobenzyl                                                 699  4-Fluorophenyl                                                                          2-Chlorobenzyl                                                 700  4-Fluorophenyl                                                                          3-Chlorobenzyl                                                 701  4-Fluorophenyl                                                                          4-Chlorobenzyl                                                 702  4-Fluorophenyl                                                                          2,4-Dichlorobenzyl                                             703  4-Fluorophenyl                                                                          2-Chloro-4-fluorobenzyl                                        704  4-Fluorophenyl                                                                          2-Pyridyl                                                      705  4-Fluorophenyl                                                                          3-Pyridyl                                                      706  4-Fluorophenyl                                                                          4-Pyridyl                                                      707  4-Fluorophenyl                                                                          5-Methyl-2-pyridyl                                             708  4-Fluorophenyl                                                                          6-Methyl-2-pyridyl                                             709  4-Fluorophenyl                                                                          6-Chloro-3-pyridyl                                             710  4-Fluorophenyl                                                                          5-Pyrimidinyl                                                  711  4-Fluorophenyl                                                                          2-Pyrazinyl                                                    712  4-Fluorophenyl                                                                          2-Thienyl                                                      713  4-Fluorophenyl                                                                          3-Thienyl                                                      714  4-Fluorophenyl                                                                          2-Furyl                                                        715  4-Fluorophenyl                                                                          3-Furyl                                                        716  4-Chlorophenyl                                                                          Phenyl                                                         717  4-Chlorophenyl                                                                          2-Methylphenyl                                                 718  4-Chlorophenyl                                                                          3-Methylphenyl                                                 719  4-Chlorophenyl                                                                          4-Methylphenyl                                                 720  4-Chlorophenyl                                                                          2,4-Dimethylphenyl                                             721  4-Chlorophenyl                                                                          2,6-Dimethylphenyl                                             722  4-Chlorophenyl                                                                          2,4,6-Trimethylphenyl                                          723  4-Chlorophenyl                                                                          4-Ethylphenyl                                                  724  4-Chlorophenyl                                                                          4-Isopropylphenyl                                              725  4-Chlorophenyl                                                                          4-tert-Butylphenyl                                             726  4-Chlorophenyl                                                                          1-Naphthyl                                                     727  4-Chlorophenyl                                                                          2-Naphthyl                                                     728  4-Chlorophenyl                                                                          4-Biphenyl                                                     729  4-Chlorophenyl                                                                          4-(2'-Chlorobiphenyl)                                          730  4-Chlorophenyl                                                                          4-(4'-Chlorobiphenyl)                                          731  4-Chlorophenyl                                                                          2-Methoxyphenyl                                                732  4-Chlorophenyl                                                                          3-Methoxyphenyl                                                733  4-Chlorophenyl                                                                          4-Methoxyphenyl                                                734  4-Chlorophenyl                                                                          3,4-Dimethoxyphenyl                                            735  4-Chlorophenyl                                                                          3,4,5-Trimethoxyphenyl                                         736  4-Chlorophenyl                                                                          4-tert-Butoxyphenyl                                            737  4-Chlorophenyl                                                                          2-Trifluoromethylphenyl                                        738  4-Chlorophenyl                                                                          3-Trifluoromethylphenyl                                        739  4-Chlorophenyl                                                                          4-Trifluoromethylphenyl                                        740  4-Chlorophenyl                                                                          4-Difluoromethoxyphenyl                                        741  4-Chlorophenyl                                                                          4-Trifluoromethoxyphenyl                                       742  4-Chlorophenyl                                                                          4-Tetrafluoroethoxyphenyl                                      743  4-Chlorophenyl                                                                          2-Fluorophenyl                                                 744  4-Chlorophenyl                                                                          3-Fluorophenyl                                                 745  4-Chlorophenyl                                                                          4-Fluorophenyl                                                 746  4-Chlorophenyl                                                                          2,4-Difluorophenyl                                             747  4-Chlorophenyl                                                                          2-Chlorophenyl                                                 748  4-Chlorophenyl                                                                          3-Chlorophenyl                                                 749  4-Chlorophenyl                                                                          4-Chlorophenyl                                                 750  4-Chlorophenyl                                                                          2,4-Dichlorophenyl                                             751  4-Chlorophenyl                                                                          3,4-Dichlorophenyl                                             752  4-Chlorophenyl                                                                          3,5-Dichlorophenyl                                             753  4-Chlorophenyl                                                                          2,4,6-Trichlorophenyl                                          754  4-Chlorophenyl                                                                          2-Chloro-4-fluorophenyl                                        755  4-Chlorophenyl                                                                          4-Chloro-2-fluorophenyl                                        756  4-Chlorophenyl                                                                          4-Bromophenyl                                                  757  4-Chlorophenyl                                                                          Benzyl                                                         758  4-Chlorophenyl                                                                          2-Methylbenzyl                                                 759  4-Chlorophenyl                                                                          4-Methylbenzyl                                                 760  4-Chlorophenyl                                                                          2,4-Dimethylbenzyl                                             761  4-Chlorophenyl                                                                          2-Fluorobenzyl                                                 762  4-Chlorophenyl                                                                          3-Fluorobenzyl                                                 763  4-Chlorophenyl                                                                          4-Fluorobenzyl                                                 764  4-Chlorophenyl                                                                          2-Chlorobenzyl                                                 765  4-Chlorophenyl                                                                          3-Chlorobenzyl                                                 766  4-Chlorophenyl                                                                          4-Chlorobenzyl                                                 767  4-Chlorophenyl                                                                          2,4-Dichlorobenzyl                                             768  4-Chlorophenyl                                                                          2-Chloro-4-fluorobenzyl                                        769  4-Chlorophenyl                                                                          2-Pyridyl                                                      770  4-Chlorophenyl                                                                          3-Pyridyl                                                      771  4-Chlorophenyl                                                                          4-Pyridyl                                                      772  4-Chlorophenyl                                                                          5-Methyl-2-pyridyl                                             773  4-Chlorophenyl                                                                          6-Methyl-2-pyridyl                                             774  4-Chlorophenyl                                                                          6-Chloro-3-pyridyl                                             775  4-Chlorophenyl                                                                          5-Pyrimidinyl                                                  776  4-Chlorophenyl                                                                          2-Pyrazinyl                                                    777  4-Chlorophenyl                                                                          2-Thienyl                                                      778  4-Chlorophenyl                                                                          3-Thienyl                                                      779  4-Chlorophenyl                                                                          2-Furyl                                                        780  4-Chlorophenyl                                                                          3-Furyl                                                        781  2,4-Dichlorophenyl                                                                      Phenyl                                                         782  2,4-Dichlorophenyl                                                                      2-Methylphenyl                                                 783  2,4-Dichlorophenyl                                                                      3-Methylphenyl                                                 784  2,4-Dichlorophenyl                                                                      4-Methylphenyl                                                 785  2,4-Dichlorophenyl                                                                      2,4-Dimethylphenyl                                             786  2,4-Dichlorophenyl                                                                      2,6-Dimethylphenyl                                             787  2,4-Dichlorophenyl                                                                      2,4,6-Trimethylphenyl                                          788  2,4-Dichlorophenyl                                                                      4-Ethylphenyl                                                  789  2,4-Dichlorophenyl                                                                      4-Isopropylphenyl                                              790  2,4-Dichlorophenyl                                                                      4-tert-Butylphenyl                                             791  2,4-Dichlorophenyl                                                                      1-Naphthyl                                                     792  2,4-Dichlorophenyl                                                                      2-Naphthyl                                                     793  2,4-Dichlorophenyl                                                                      4-Biphenyl                                                     794  2,4-Dichlorophenyl                                                                      4-(2'-Chlorobiphenyl)                                          795  2,4-Dichlorophenyl                                                                      4-(4'-Chlorobiphenyl)                                          796  2,4-Dichlorophenyl                                                                      2-Methoxyphenyl                                                797  2,4-Dichlorophenyl                                                                      3-Methoxyphenyl                                                798  2,4-Dichlorophenyl                                                                      4-Methoxyphenyl                                                799  2,4-Dichlorophenyl                                                                      3,4-Dimethoxyphenyl                                            800  2,4-Dichlorophenyl                                                                      3,4,5-Trimethoxyphenyl                                         801  2,4-Dichlorophenyl                                                                      4-tert-Butoxyphenyl                                            802  2,4-Dichlorophenyl                                                                      2-Trifluoromethylphenyl                                        803  2,4-Dichlorophenyl                                                                      3-Trifluoromethylphenyl                                        804  2,4-Dichlorophenyl                                                                      4-Trifluoromethylphenyl                                        805  2,4-Dichlorophenyl                                                                      4-Difluoromethoxyphenyl                                        806  2,4-Dichlorophenyl                                                                      4-Trifluoromethoxyphenyl                                       807  2,4-Dichlorophenyl                                                                      4-Tetrafluoroethoxyphenyl                                      808  2,4-Dichlorophenyl                                                                      2-Fluorophenyl                                                 809  2,4-Dichlorophenyl                                                                      3-Fluorophenyl                                                 810  2,4-Dichlorophenyl                                                                      4-Fluorophenyl                                                 811  2,4-Dichlorophenyl                                                                      2,4-Difluorophenyl                                             812  2,4-Dichlorophenyl                                                                      2-Chlorophenyl                                                 813  2,4-Dichlorophenyl                                                                      3-Chlorophenyl                                                 814  2,4-Dichlorophenyl                                                                      4-Chlorophenyl                                                 815  2,4-Dichlorophenyl                                                                      2,4-Dichlorophenyl                                             816  2,4-Dichlorophenyl                                                                      3,4-Dichlorophenyl                                             817  2,4-Dichlorophenyl                                                                      3,5-Dichlorophenyl                                             818  2,4-Dichlorophenyl                                                                      2,4,6-Trichlorophenyl                                          819  2,4-Dichlorophenyl                                                                      2-Chloro-4-fluorophenyl                                        820  2,4-Dichlorophenyl                                                                      4-Chloro-2-fluorophenyl                                        821  2,4-Dichlorophenyl                                                                      4-Bromophenyl                                                  822  2,4-Dichlorophenyl                                                                      Benzyl                                                         823  2,4-Dichlorophenyl                                                                      2-Methylbenzyl                                                 824  2,4-Dichlorophenyl                                                                      4-Methylbenzyl                                                 825  2,4-Dichlorophenyl                                                                      2,4-Dimethylbenzyl                                             826  2,4-Dichlorophenyl                                                                      2-Fluorobenzyl                                                 827  2,4-Dichlorophenyl                                                                      3-Fluorobenzyl                                                 828  2,4-Dichlorophenyl                                                                      4-Fluorobenzyl                                                 829  2,4-Dichlorophenyl                                                                      2-Chlorobenzyl                                                 830  2,4-Dichlorophenyl                                                                      3-Chlorobenzyl                                                 831  2,4-Dichlorophenyl                                                                      4-Chlorobenzyl                                                 832  2,4-Dichlorophenyl                                                                      2,4-Dichlorobenzyl                                             833  2,4-Dichlorophenyl                                                                      2-Chloro-4-fluorobenzyl                                        834  2,4-Dichlorophenyl                                                                      2-Pyridyl                                                      835  2,4-Dichlorophenyl                                                                      3-Pyridyl                                                      836  2,4-Dichlorophenyl                                                                      4-Pyridyl                                                      837  2,4-Dichlorophenyl                                                                      5-Methyl-2-pyridyl                                             838  2,4-Dichlorophenyl                                                                      6-Methyl-2-pyridyl                                             839  2,4-Dichlorophenyl                                                                      6-Chloro-3-pyridyl                                             840  2,4-Dichlorophenyl                                                                      5-Pyrimidinyl                                                  841  2,4-Dichlorophenyl                                                                      2-Pyrazinyl                                                    842  2,4-Dichlorophenyl                                                                      2-Thienyl                                                      843  2,4-Dichlorophenyl                                                                      3-Thienyl                                                      844  2,4-Dichlorophenyl                                                                      2-Furyl                                                        845  2,4-Dichlorophenyl                                                                      3-Furyl                                                        846  4-Methoxyphenyl                                                                         Phenyl                                                         847  4-Methoxyphenyl                                                                         2-Methylphenyl                                                 848  4-Methoxyphenyl                                                                         3-Methylphenyl                                                 849  4-Methoxyphenyl                                                                         4-Methylphenyl                                                 850  4-Methoxyphenyl                                                                         2,4-Dimethylphenyl                                             851  4-Methoxyphenyl                                                                         2,6-Dimethylphenyl                                             852  4-Methoxyphenyl                                                                         2,4,6-Trimethylphenyl                                          853  4-Methoxyphenyl                                                                         4-Ethylphenyl                                                  854  4-Methoxyphenyl                                                                         4-Isopropylphenyl                                              855  4-Methoxyphenyl                                                                         4-tert-Butylphenyl                                             856  4-Methoxyphenyl                                                                         1-Naphthyl                                                     857  4-Methoxyphenyl                                                                         2-Naphthyl                                                     858  4-Methoxyphenyl                                                                         4-Biphenyl                                                     859  4-Methoxyphenyl                                                                         4-(2'-Chlorobiphenyl)                                          860  4-Methoxyphenyl                                                                         4-(4'-Chlorobiphenyl)                                          861  4-Methoxyphenyl                                                                         2-Methoxyphenyl                                                862  4-Methoxyphenyl                                                                         3-Methoxyphenyl                                                863  4-Methoxyphenyl                                                                         4-Methoxyphenyl                                                864  4-Methoxyphenyl                                                                         3,4-Dimethoxyphenyl                                            865  4-Methoxyphenyl                                                                         3,4,5-Trimethoxyphenyl                                         866  4-Methoxyphenyl                                                                         4-tert-Butoxyphenyl                                            867  4-Methoxyphenyl                                                                         2-Trifluoromethylphenyl                                        868  4-Methoxyphenyl                                                                         3-Trifluoromethylphenyl                                        869  4-Methoxyphenyl                                                                         4-Trifluoromethylphenyl                                        870  4-Methoxyphenyl                                                                         4-Difluoromethoxyphenyl                                        871  4-Methoxyphenyl                                                                         4-Trifluoromethoxyphenyl                                       872  4-Methoxyphenyl                                                                         4-Tetrafluoroethoxyphenyl                                      873  4-Methoxyphenyl                                                                         2-Fluorophenyl                                                 874  4-Methoxyphenyl                                                                         3-Fluorophenyl                                                 875  4-Methoxyphenyl                                                                         4-Fluorophenyl                                                 876  4-Methoxyphenyl                                                                         2,4-Difluorophenyl                                             877  4-Methoxyphenyl                                                                         2-Chlorophenyl                                                 878  4-Methoxyphenyl                                                                         3-Chlorophenyl                                                 879  4-Methoxyphenyl                                                                         4-Chlorophenyl                                                 880  4-Methoxyphenyl                                                                         2,4-Dichlorophenyl                                             881  4-Methoxyphenyl                                                                         3,4-Dichlorophenyl                                             882  4-Methoxyphenyl                                                                         3,5-Dichlorophenyl                                             883  4-Methoxyphenyl                                                                         2,4,6-Trichlorophenyl                                          884  4-Methoxyphenyl                                                                         2-Chloro-4-fluorophenyl                                        885  4-Methoxyphenyl                                                                         4-Chloro-2-fluorophenyl                                        886  4-Methoxyphenyl                                                                         4-Bromophenyl                                                  887  4-Methoxyphenyl                                                                         Benzyl                                                         888  4-Methoxyphenyl                                                                         2-Methylbenzyl                                                 889  4-Methoxyphenyl                                                                         4-Methylbenzyl                                                 890  4-Methoxyphenyl                                                                         2,4-Dimethylbenzyl                                             891  4-Methoxyphenyl                                                                         2-Fluorobenzyl                                                 892  4-Methoxyphenyl                                                                         3-Fluorobenzyl                                                 893  4-Methoxyphenyl                                                                         4-Fluorobenzyl                                                 894  4-Methoxyphenyl                                                                         2-Chlorobenzyl                                                 895  4-Methoxyphenyl                                                                         3-Chlorobenzyl                                                 896  4-Methoxyphenyl                                                                         4-Chlorobenzyl                                                 897  4-Methoxyphenyl                                                                         2,4-Dichlorobenzyl                                             898  4-Methoxyphenyl                                                                         2-Chloro-4-fluorobenzyl                                        899  4-Methoxyphenyl                                                                         2-Pyridyl                                                      900  4-Methoxyphenyl                                                                         3-Pyridyl                                                      901  4-Methoxyphenyl                                                                         4-Pyridyl                                                      902  4-Methoxyphenyl                                                                         5-Methyl-2-pyridyl                                             903  4-Methoxyphenyl                                                                         6-Methyl-2-pyridyl                                             904  4-Methoxyphenyl                                                                         6-Chloro-3-pyridyl                                             905  4-Methoxyphenyl                                                                         5-Pyrimidinyl                                                  906  4-Methoxyphenyl                                                                         2-Pyrazinyl                                                    907  4-Methoxyphenyl                                                                         2-Thienyl                                                      908  4-Methoxyphenyl                                                                         3-Thienyl                                                      909  4-Methoxyphenyl                                                                         2-Furyl                                                        910  4-Methoxyphenyl                                                                         3-Furyl                                                        __________________________________________________________________________

The abovementioned compounds 1a where Ar is 3-pyridyl are also inprinciple obtainable for those where Ar is 5-pyrimidinyl, 2-pyrazinyl or3-pyridazinyl as in the abovementioned synthesis examples.

The novel hetarylalkenes I have excellent activity against a broadspectrum of phytopathogenic fungi, in particular from the classconsisting of the Ascomycetes and Basidiomycetes. Some of them havesystemic activity and can be used as foliage or soil fungicides. Theyare of particular interest for controlling a large number of fungi onvarious crops or their seeds, in particular wheat, rye, barley, oats,rice, corn, lawns, cotton, soybean, coffee, sugar cane, fruit andornamentals in horticulture, in viticulture and on vegetables, such ascucumbers, beans and cucurbitaceae.

The novel hetarylalkenes are particularly suitable for controlling thefollowing harmful fungi:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearumand Sphaerotheca fuliginea in cucurbitaceae,

Podosphaera leucotricha in apples,

Uncinula necator on grapevines,

Puccinia species on cereals,

Rhizoctonia species on cotton and lawns,

Ustilago species on cereals and sugar cane,

Venturia inaequalis (scab) on apples,

Helminthosporium species on cereals,

Septoria nodorum on wheat,

Botrytis cinerea (gray mold) on strawberries and grapevines,

Cercospora arachidicola on peanuts,

Pseudocercosporella herpotrichoides on wheat and barley,

Pyricularia oryzae on rice,

Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on various plants,

Plasmopara viticola on grapevines and

Alternaria species on vegetables and fruit.

The hetarylalkenes are used by spraying or dusting the plants, materialsor areas with the active ingredients or treating the seeds of the plantswith the active ingredients. Application is effected before or afterinfection with the fungi.

The hetarylalkenes can be converted into the conventional fungicides(formulations), i.e. into solutions, emulsions, suspensions, dusts,powders, pastes and granules. The application forms depend entirely onthe intended uses; they should in any case ensure a fine and uniformdistribution of the active substance. The formulations are prepared in aknown manner and using the conventional assistants, for example byextending the active ingredient with solvents and/or carriers, ifnecessary with the use of emulsifiers and dispersants. Suitableassistants for this purpose are essentially solvents, such as aromatics(e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins(e.g. mineral oil fractions), alcohols (e.g. methanol or butanol),ketones (e.g. cyclohexanone), amines (e.g. ethanolamine ordimethylformamide) and water (the latter if necessary together withorganic solvents); carriers, such as ground natural minerals (e.g.kaolins, clays, talc or chalk) and ground synthetic minerals (eg. finelydivided silica or silicates; emulsifiers, such as ionic and anionicemulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonatesand arylsulfonates) and dispersants, such as ligninsulfite waste liquorsand methylcellulose.

The fungicides generally contain from 0.1 to 95, preferably from 0.5 to90, % by weight of active ingredient. The application rates are from0.02 to 3 kg of active ingredient per ha, depending on the type ofeffect desired.

The agents, if necessary after further dilution, are applied in a knownmanner, for example by spraying, atomizing, dusting, broadcasting,dressing or pouring.

Examples of formulations are:

I. 90 parts by weight of compound No. 66 are mixed with 10 parts byweight of N-methyl-α-pyrrolidone, and a solution which is suitable foruse in the form of very small drops is obtained.

II. 20 parts by weight of compound No. 71 are dissolved in a mixturewhich consists of 80 parts by weight of xylene, 10 parts by weight ofthe adduct of from 8 to 10 moles of ethylene oxide with 1 mole of oleicacid N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40moles of ethylene oxide with 1 mole of castor oil. By pouring thesolution into water and finely distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound No. 72 are dissolved in a mixturewhich consists of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol and 20 parts by weight of the adduct of 40 moles ofethylene oxide with 1 mole of castor oil. By pouring the solution intowater and finely distributing it therein, an aqueous dispersion isobtained.

IV. 20 parts by weight of compound No. 99 are dissolved in a mixturewhich consists of 25 parts by weight of cyclohexanol, 65 parts by weightof a mineral oil fraction boiling within a range from 210° to 280° C.and 10 parts by weight of the adduct of 40 moles of ethylene oxide with1 mole of castor oil. By pouring the solution into water and finelydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound No. 131 are thoroughly mixed with 3parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 10 parts by weight of the sodium salt of a ligninsulfonic acidfrom a sulfite waste liquor and 7 parts by weight of silica gel powder,and the mixture is milled in a hammer mill. By finely distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound No. 132 are thoroughly mixed with 97parts by weight of finely divided kaolin. A dusting agent which contains3% by weight of the active ingredient is obtained in this manner.

VII. 30 parts by weight of compound No. 134 are thoroughly mixed with amixture consisting of 92 parts by weight of silica gel powder and 8parts by weight of liquid paraffin, which has been sprayed onto thesurface of this silica gel. A formulation of the active ingredienthaving good adhesion is obtained in this manner.

VIII. 40 parts by weight of compound No. 135 are thoroughly mixed with10 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate, 2 parts by weight of silica gel and48 parts by weight of water. A stable aqueous dispersion is obtained. Anaqueous dispersion is obtained by dilution with water.

IX. 20 parts by weight of compound No. 136 are thoroughly mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the novel agents may also be presenttogether with other active ingredients, for example herbicides,insecticides, growth regulators and fungicides, or may be mixed withfertilizers and applied together with them. Mixing with fungicidesresults, in many cases, in an extension of the fungicidal actionspectrum.

The following list of fungicides with which the novel compounds may becombined is intended to illustrate the possible combinations but not toimpose any restrictions.

Sulfur,

dithiocarbamates and their derivatives, such as

ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediamine bisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-propylenebis-(thiocarbamoyl) disulfide;

nitro derivatives, such as

dinitro-(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate and diisopropyl5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecyl-2-imidazoline acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothioate,

5-amino-1-[bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio-(4,5-b)-quinoxaline,

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-fur-2-ylbenzimidazole,

2-thiazol-4-ylbenzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthio tetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N°,N°-dimethyl-N-phenyl-sulfuric aciddiamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylbenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,pyridine-2-thio-1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4dioxide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,

2-methylfuran-3-carboxanilide,

2,5-dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethylfuran-3-carboxylic acid cyclohexylamide,

N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,

N-[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine,

1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,

1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2ylethyl]-1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazol-ylurea,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene and

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

and various other fungicides, such as

dodecylguanidine acetate,

3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutarimide,

hexachlorobenzene,

methyl DL-N-(2,6-dimethylphenyl)-N-2-furoylalaninate,

methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanine,

N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanine,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3-(3,5-dichlorophenyl )-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,

1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2-4-triazole,

2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridineand

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

EXAMPLES OF USE

The fungicidal action of the hetarylalkenes I was compared with that of2-(2,4-dichlorophenyl)-3-(3-pyridyl)-acrylic acid (A), disclosed inEP-A2-104 690, and 1(4-chlorophenyl)-3-(3-pyridyl)-prop-2-en-1-one (B),disclosed under CAS-Reg. No. 40665-19-8, in greenhouse experiments.

EXAMPLE A Activity against Pyrenophora teres

The experiments were carried out using the active ingredients 66, 71,72, 99, 100, 134, 135, 136, 137, 143, 262, 265, 273, 360, 490 and 555.

Barley seedlings of the Igri variety, in the two-leaf stage, weresprayed to run-off with aqueous suspensions which contained 80% ofactive ingredient and 20% of emulsifier, the percentages being based ondry substance. After 24 hours, the plants were inoculated with a sporesuspension of the fungus Pyrenophora teres and were placed for 48 hoursin a conditioned chamber at high atmospheric humidity and at 18° C.Thereafter, the plants were cultivated for a further 5 days in agreenhouse at 20°-22° C. and 70% relative humidity. The extent ofdevelopment of the symptoms was then determined.

The result shows that, when applied as a 0.05% strength sprayformulation, all active ingredients investigated have a betterfungicidal action (90%) than the known comparative active ingredient (A)(40%).

EXAMPLE B Activity against powdery mildew of cucumbers

The experiments were carried out using the active ingredients 295, 360,490 and 555.

Young cucumber plants of the Chinesische Schlange variety, in thetwo-leaf stage, were sprayed with an aqueous conidia suspension ofcucumber powdery mildew (Erysiphe cichoracearum and Sphaerothecafuliginea). On the next day, these plants were sprayed to run-off withan aqueous spray liquor which contained 80% of active ingredient and 20%of emulsifier, the percentages being based on dry substance, and wereplaced in a greenhouse at from 20° to 22° C. and from 70 to 70%humidity. 21 days after application of the active ingredient, the extentof fungal attack was determined.

The result shows that, when applied as a 0.025% strength aqueous activeingredient formulation, all active ingredients investigated have betterfungicidal action (95%) than the known comparative active ingredient (B)(0%).

EXAMPLE C Activity against Botrytis cinerea

The experiments were carried out using the active ingredients 72, 136,265, 273, 490 and 555.

After 4 or 5 leaves were well developed, pimento seedlings of theNeusiedler Ideal Elite variety were sprayed to run-off with aqueoussuspensions which contained 80% of active ingredient and 20% ofemulsifier, the percentages being based on dry substance. After thespray coating had dried off, the plants were sprayed with a conidiasuspension of the fungus Botrytis cinerea and were placed in a chamberat high humidity and at from 22° to 24° C. After 5 days, the disease haddeveloped on the untreated control plants to such an extent that theresulting leaf necroses covered the predominant part of the leaves.

The result shows that, when applied as a 0.05% strength aqueous activeingredient formulation, all active ingredients investigated have abetter fungicidal action (90%) than the known comparative activeingredient (A) (40%).

We claim:
 1. A hetarylalkene of the formula I ##STR12## where Ar is3-pyridyl;A is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₈ -cycloalkyl, C₃-C₈ -cycloalkyl-C₁ -C₃ -alkyl or phenyl or phenyl or phenylalkyl, wherephenyl in each case may be mono-substituted, disubstituted, ortrisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -mono, di- ortrihaloalkyl, C₁ -C₄ -haloalkoxy, phenyl or halogen: Z is ##STR13##where R is hydrogen, C₁ -C₄ -alkyl, C₂ -C₄ -acyl, phenyl, benzyl orbenzoyl, in which each of the phenyl rings may be monosubstituted,disubstituted or trisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, halogen, cyano or nitro, or R is C₁ -C₄-alkylsulfonyl or unsubstituted or C₁ -C₄ -alkyl-substitutedphenylsulfonyl,R¹ is C₁ -C₄ -alkyl, phenyl or benzyl, where each of thephenyl rings may be mono-substituted, disubstituted or trisubstituted byC₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy,halogen, cyano or nitro, and Hal is fluorine, chlorine, bromine oriodine; and B is aryl, or aralkyl wherein aryl in each case may bephenyl or naphthyl and in which each of the aromatic rings may bemono-substituted, disubstituted or trisubstituted by C₁ -C₄ -alkyl, C₁-C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, phenyl, halophenyl or halogen, andits N-oxides and addition salts with inorganic mineral acids, carboxylicacids or mononuclear aryl-sulfonic acids.
 2. A hetarylalkenal of theformula III ##STR14## where Ar is 3-pyridyl and D is C₂ -C₆ -alkyl, C₃-C₈ -cycloalkyl, C₃ -C₈ -cycloalkyl-C₁ -C₃ -alkyl or mononuclear ordinuclear aryl C₁ -C₃ -alkyl, in which aryl may be mono-substituted,disubstituted, or trisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, phenyl or halogen.
 3. A fungicidecontaining a hetarylalkene, an N-oxide or an acid addition salt asclaimed in claim 1 and conventional additives.
 4. A method forcontrolling harmful fungi, wherein the fungi or the plants, seeds,materials, or areas threatened by fungal attack are treated with afungicidally effective amount of a hetarylalkene of the formula I'##STR15## where Ar is 3-pyridyl;A is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃-C₈ -cycloalkyl, C₃ -C₈ -cycloalkyl-C₁ -C₃ -alkyl or phenyl orphenylalkyl, where phenyl in each case may be mono-substituted,disubstituted, or trisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁-C₄ -mono-, di- or trihaloalkyl, C₁ -C₄ -haloalkoxy, phenyl or halogen:Z is ##STR16## where R is hydrogen, C₁ -C₄ -alkyl, C₂ -C₄ -acyl, phenyl,benzyl or benzoyl, in which each of the phenyl rings may bemonosubstituted, disubstituted or trisubstituted by C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, halogen, cyano ornitro, or R is C₁ -C₄ -alkylsulfonyl or unsubstituted or C₁ -C₄-alkyl-substituted phenylsulfonyl,R¹ is C₁ -C₄ -alkyl, phenyl or benzyl,where each of the phenyl rings may be mono-substituted, disubstituted ortrisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁-C₄ -haloalkoxy, halogen, cyano or nitro, and Hal is fluorine, chlorine,bromine or iodine; and B₁ is aryl, or aralkyl wherein aryl in each casemay be phenyl or naphthyl and in which each of the aromatic rings may bemono-substituted, disubstituted or trisubstituted by C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, phenyl, halophenylor halogen, and its N-oxides and addition salts with inorganic mineralacids, carboxylic acids or mononuclear aryl-sulfonic acids; or with afungicide containing a hetarylalkene of formula I' as defined above, anN-oxide or an acid addition salt and conventional additives.